Cationic polyglyceryl compositions and compounds

ABSTRACT

Provided are polyglyceryl compositions comprising one or more polyglyceryl compounds having: (a) a node structure comprising at least three contiguous glyceryl remnant units; (b) one or more cationic groups each linked to the node structure by an independently selected linking group; and (c) one or more hydrophobic moieties each independently (i) linked to the node structure by a linking group, or (ii) constituting a portion of one of the one or more cationic groups, wherein the composition has an average degree of polymerization determined by hydroxyl value testing (DP OH ) of from about 3 to about 20. Also provided are polyglyceryl compounds which may compose such compositions, and uses of the polyglyceryl compositions and compounds.

FIELD OF INVENTION

The present invention relates to cationic polyglyceryl compositions andcompounds that are useful in a variety of applications includingmoisturizing or conditioning the skin or hair.

DESCRIPTION OF THE RELATED ART

Personal care compositions, e.g., lotions, conditioners, cleansers andthe like, typically include numerous ingredients. These ingredients maybe used to stabilize the product, provide improved aesthetics, as wellas moisturize, condition, cleanse or otherwise treat the body. Forexample, so-called “humectants” are a class of ingredients whichgenerally serve to attract moisture and retard evaporation of water fromthe body surface. Common commercial humectants include glycerin,propylene glycol, sorbitols, and polyethylene glycols.

The inventors have recognized that in order to increase the optionsavailable to designers of personal care products, it would be desirableto have a humectant material that has additional functionality, such asone or more of improved substantivity, moisture retention, foaming,viscosity building, and mildness. Furthermore, the inventors haveadditionally recognized that it would be desirable to be able to tunethese various properties by adjusting the proportions and chemistry ofthe reactants used to make the humectant material. Additionally, theinventors have recognized that it would beneficial for the process ofmaking such a material not to require an ethoxylation process, due tothe potential health and safety risks of working with ethylene oxidestarting material.

Accordingly, the invention described herein addresses one or more of theabove-mentioned drawbacks.

SUMMARY OF THE INVENTION

The present invention provides cationic polyglyceryl compounds thatovercome the disadvantages of the prior art and tend to exhibitbeneficial unexpected properties. In particular, applicants havediscovered that the compositions and compounds of the present inventiontend to exhibit improved substantivity, moisture retention, foaming,viscosity building, mildness, and/or combinations thereof, as comparedto other comparable (polyglyceryl or otherwise) humectant compounds.

According to one aspect, the present invention provides polyglycerylcompositions comprising one or more polyglyceryl compounds having: (a) anode structure comprising at least three contiguous glyceryl remnantunits; (b) one or more cationic groups each linked to the node structureby an independently selected linking group; and (c) one or morehydrophobic moieties each independently (i) linked to the node structureby a linking group, or (ii) constituting a portion of one of the one ormore cationic groups.

According to another aspect, the present invention provides polyglycerylcompounds comprising one or more compounds, of the Formula I:

wherein, according to this embodiment:

-   -   Z is a polyglyceryl node structure that comprises at least 3        contiguous glyceryl remnant units;    -   Nu are independently selected nucleophilic groups which are        directly linked to Z;    -   d is the number of nucleophilic groups directly bonded to Z, and        is from 2 to 21;    -   L₁ is an independently selected linking group which links Z to        Hphob₁;    -   Hphob₁ is an independently selected hydrophobic moiety        comprising 6 to 30 carbons;    -   a is the number of Hphob₁ linked to the node structure Z, each        via an L₁, and is from zero to 10;    -   L₂ is an independently selected linking group which links Z to a        cationic group —R₁—N—[(R₂)(R₃)(Hphob₂)];    -   R₁ is an independently selected linear or branched alkylene        (—CH— to —C₆H₁₂—) or monohydroxyalkylene (—CH(OH)— to        —C₆H₁₁(OH)—);    -   N is a nitrogen atom;    -   R₂ is an independently selected alkyl group containing 1 to 4        carbons (CH₃ to C₄H₉) or a hydrogen atom;    -   R₃ is an independently selected alkyl group containing 1 to 4        carbons (CH₃ to C₄H₉) or a hydrogen atom, or an independently        selected hydrophobic moiety;    -   Hphob₂ is an independently selected hydrophobic moiety        comprising 6 to 30 carbons;    -   X₁ is an anionic counterion or absent;    -   b is the number of (R₁—N—[(R₂)(R₃)(Hphob₂)]) linked to the node        structure, Z, each via an L₂, and is from zero to 10;    -   L₃ is an independently selected linking group which links Z to        cationic group —R₄—N—[(R₅)(R₆)(R₇)];    -   R₄ is an independently selected linear or branched alkylene        (—CH— to —C₆H₁₂—) or monohydroxylalkylene (—CH(OH)— to        —C₆(OH)H₁₁(OH)—);    -   R₅, R₆, R₇ are each an independently selected alkyl group        containing 1 to 4 carbons (CH₃ to C₄H₉);    -   X₂ is a anionic counterion or absent;    -   c is the number of (R₄—N—[(R₅)(R₆)(R₇)]) linked to the node        structure, Z, each via an L₃, and is from zero to 10;    -   wherein the sum of a and b is from 1 to 10 inclusive;    -   the sum of b and c is from 1 to 10 inclusive;    -   the sum of a, b, and c is from 1 to 10 inclusive;    -   and the sum of a, b, c and d is from 3 to 22 inclusive.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical depiction of zero shear viscosities of certaincompositions of the present invention and comparable compositions.

FIG. 2 is a graphical depiction of hydroxyl value verses the degree ofpolymerization for a linear polyglycerol.

FIG. 3 is a graphical depiction of maximum foam volume and foam volumevalues of certain compositions of the present invention and comparablecompositions.

FIG. 4 is a graphical depiction of the relative viscosities of certaincompositions of the present invention and comparable compositions.

DESCRIPTION OF PREFERRED EMBODIMENTS

All percentages listed in this specification are percentages ofsolids/active amounts by weight, unless otherwise specificallymentioned.

As used herein, the term “healthcare” refers to the fields of personalcare and medical care including, but not limited to, infant care, oralcare, sanitary protection, skin care, including the topical treatment ofadult or infant skin to maintain the health of the skin, improve thehealth of the skin, and/or improve the appearance of the skin, woundcare, including the treatment of a wound to assist in the closure orhealing of a wound, and/or to reduce the pain or scarring associatedwith the wound, women's health, including the treatment of tissue in theinternal or external vaginal area and/or breast, maintaining orimproving the health of such tissue or skin, repairing such tissue orskin, reducing irritation of such tissue or skin, maintaining orimproving the appearance of such tissue or skin, and improving orenhancing sexual function associated with such tissue or skin, and thelike.

As noted above, applicants have discovered that certain cationicpolyglyceryl compositions can be used as nonethoxylated, substantivehumectants in various compositions, including cosmetic and personal carecompositions. The resulting compositions may be suitable for use ascleansing, rinse-off, or leave-on compositions. In particular,applicants have recognized significant unexpected benefits associatedwith compositions comprising one or more polyglyceryl compounds having:(a) a node structure comprising at least three contiguous glycerylremnant units; (b) one or more cationic groups each linked to the nodestructure by an independently selected linking group; and (c) one ormore hydrophobic moieties each independently (i) linked to the nodestructure by a linking group, or (ii) constituting a portion of one ofthe one or more cationic groups.

In certain embodiments of the instant invention, the cationicpolyglyceryl compositions comprise at least one polyglyceryl compound asdescribed herein, preferably two or more. In certain embodiments, thepolyglyceryl compositions of the present invention comprise at leastthree, preferably at least four, and in certain preferred embodiments,at least five polyglyceryl compounds as described herein. In suchembodiments, the polyglyceryl composition preferably has an averagedegree of polymerization determined by hydroxyl value testing (DP_(OH))of from about 3 to about 20, for example, from about 3 to about 18, orfrom about 3 to about 15. In certain preferred embodiments, thepolyglyceryl compositions of the present invention have a DP_(OH) offrom about 3 to about 12, and even more preferably from about 3 to about10, more preferably about 5 to about 10, more preferably about 7 toabout 10, and more preferably about 10.

As described herein, the hydroxyl value (OH#) associated with apolyglyceryl material, defined as the number of milligrams of potassiumhydroxide equivalent to the hydroxyl content of one gram of sample, ismeasured in accord with the standard American Oil Chemists' Society(AOCS) Official Method Cd 13-60 Hydroxyl Value. DP_(OH) of thepolyglyceryl material is then calculated, using the hydroxyl value (OH#)of the material, in accord with the following equation:

${DP}_{OH} = \frac{{112,200} - \left( {18 \times {OH}\#} \right)}{\left( {74.05 \times {OH}\#} \right) - {56,100}}$

For the purposes of clarity only, the following general description ofhydroxyl value and DP_(OH) for a polyglyceryl material are provided. Forhydroxyl value, in accord with the AOCS method above, a known mass ofthe material to be tested (e.g. a polyglyceryl material) is reacted withacetic anhydride in the presence of pyridine. The acetylated polyol isthen hydrolyzed to the resulting polyol and acetic acid. The amount ofacetic acid released during the hydrolysis reaction is determined bytitrating KOH in the presence of a phenothalein indicator. The hydroxylvalue is then determined by calculating the mg of KOH required toneutralize the solution containing one gram of polyol. The DP_(OH) isthen calculated using the hydroxyl number via the calculation above.

Those of skill in the art will recognize that DP_(OH) is determined by atechnique which does not distinguish between linear and dendritic(branched or cyclic) repeat units, but rather provides informationregarding the number of hydroxyl groups per gram of polymer. Thoseskilled in the art will recognize that the number average DP (DP_(n)),which is based on the average number of repeating units per polymer, maydeviate significantly from the DP_(OH) if certain isomers, such ascyclic repeat units, are present (Crowther, M. W. et al., JAOCS, 75,1867, 1998). This is depicted, for example, in FIG. 2, which shows atheoretical curve of hydroxyl value vs DP_(n) for the case of purelinear polyglycerol (open squares) and a polyglycerol sample containing20 wt % cyclic repeat units. The closed symbol on each line approximatesa hydroxyl value of 900. As seen in FIG. 2, a 20/80 wt % cyclic/linearmixture which yields a hydroxyl value of 900 has a DP_(n) ofapproximately 5.5 (closed circle), as compared to a DP_(OH) of 9 (closedsquare).

According to preferred embodiments of the present invention, thecompositions of the present invention have an average degree ofsubstitution of hydrophobic moieties per node structure (e.g., “a”+“b”)that is greater than zero but less than ten, more preferably greaterthan zero but less than five, and even more preferably greater than zerobut less than or equal to three. Those skilled in the art will recognizethat substitution of a node structure with hydrophobic moieties to formcompounds/compositions of the present invention is likely aheterogeneous process which results in two or more differentlysubstituted cationic polyglyceryl compounds, and thus the average numberof hydrophobic moieties per node for a composition, may be representedby a non-integer average value. An example calculation is provided: fora composition comprising polyglyceryl homopolymer compounds of Formula I(DP_(OH)=10, i.e., having 10 glyceryl remnant units), with each polymercomprised of an independent composition of Hphob₁ and Hphob₂ moieties.If 50 mol % of the node structures, Z have 2 mol of L₁-Hphob₁, 40 mol %of the polyglyceryl remnants Z have 1 mol of L₁-Hphob₁, and 10 mol % ofthe polyglyceryl remnants Z have 0 mol of L₁-Hphob₁, then there are 1.4{2(0.5)+1(0.4)+0(0.1)=1.4} L₁-R₁-Hphob₁ per mol of Z.

According to preferred embodiments of the present invention, thecompositions of the present invention have an average degree ofsubstitution of cationic moieties per node (e.g., “b”+“c”) that isgreater than zero but less than 10, more preferably greater than zerobut less than 5, and even more preferably greater than zero but lessthan 3. An example calculation is provided: for a composition comprisingpolyglyceryl homopolymer compounds of Formula I (DP=10, i.e., having 10glyceryl remnant units), with each polymer comprised of an independentcomposition of cationic hydrophobic (—R₁—N—[(R₂)(R₃)(Hphob₂)]) andcationic (—R₄—N—[(R₅)(R₆)(R₇)]) groups. If 60 mol % of the nodestructures, Z have 2 mol of (—R₁—N—[(R₂)(R₃)(Hphob₂)]), 30 mol % of thepolyglyceryl remnants Z have 1 mol of (—R₁—N—[(R₂)(R₃)(Hphob₂)]), 10 mol% of the polyglyceryl remnants Z have 0 mol of(—R₁—N—[(R₂)(R₃)(Hphob₂)]) then there are 1.5 {2(0.6)+1(0.3)+0(0.1)=1.5}(—R₁—N—[(R₂)(R₃)(Hphob₂)]) per mol of Z. Similarly, If 20 mol % of thenode structures, Z have 2 mol of (—R₄—N—[(R₅)(R₆)(R₇)]), 50 mol % of thepolyglyceryl remnants Z have 1 mol of (—R₄—N—[(R₅)(R₆)(R₇)]), 30 mol %of the polyglyceryl remnants Z have 0 mol of (—R₄—N—[(R₅)(R₆)(R₇)]) thenthere are 0.9 {2(0.2)+1(0.5)+0(0.3)=0.9} (—R₄—N—[(R₅)(R₆)(R₇)]) per molof Z. Thus, the average degree of cationic substitution per mol of Z is2.4 {1.5+0.9=2.4}

According to preferred embodiments of the present invention, thecompositions of the present invention have an average degree ofsubstitution of cationic hydrophobic moieties per node (e.g., “b”) thatis greater than zero but less than 10, more preferably greater than zerobut less than 5, and even more preferably greater than about 0.5 butless than 3. An example calculation is provided: for a compositioncomprising polyglyceryl homopolymer compounds of Formula I (DP=10, i.e.,having 10 glyceryl remnant units), with each polymer comprised of anindependent composition of cationic hydrophobic groups(—R₁—N—[(R₂)(R₃)(Hphob₂)]). If 10 mol % of the node structures, Z have 3mol of (—R₁—N—[(R₂)(R₃)(Hphob₂)]), 30 mol % of the polyglyceryl remnantsZ have 2 mol of (—R₁—N—[(R₂)(R₃)(Hphob₂)]), 40 mol % of the polyglycerylremnants Z have 1 mol of (—R₁—N—[(R₂)(R₃)(Hphob₂)]), 20 mol % of thepolyglyceryl remnants Z have 0 mol of (—R₁—N—[(R₂)(R₃)(Hphob₂)]) thenthere are 1.3 {3(0.1)+2(0.3)+1(0.4)+0(0.2)=1.3}(—R₁—N—[(R₂)(R₃)(Hphob₂)]) per mol of Z.

According to certain embodiments, the compounds of the presentinvention, and the compositions that are made up of such compounds, maybe further illustrated with reference to Formula I:

wherein, according to this embodiment:

-   -   Z is a polyglyceryl node structure that comprises at least 3        contiguous glyceryl remnant units;    -   Nu are independently selected nucleophilic groups which are        directly linked to Z;    -   d is the number of nucleophilic groups bonded to Z, and is from        2 to 21;    -   L₁ is an independently selected linking group which links Z to        Hphob₁    -   Hphob₁ is an independently selected hydrophobic moiety        comprising 6 to 30 carbons;    -   a is the number of Hphob₁ linked to the node structure Z, each        via an L₁, and is from zero to 10;    -   L₂ is an independently selected linking group which links Z to a        cationic group —R₁—N—[(R₂)(R₃)(Hphob₂)];    -   R₁ is an independently selected linear or branched alkylene        (—CH— to —C₆H₁₂—) or monohydroxyalkylene (—CH(OH)— to        —C₆H₁₁(OH)—);    -   N is a nitrogen atom;    -   R₂ is an independently selected alkyl group containing 1 to 4        carbons (CH₃ to C₄H₉) or a hydrogen atom;    -   R₃ is an independently selected alkyl group containing 1 to 4        carbons (CH₃ to C₄H₉) or a hydrogen atom, or an independently        selected hydrophobic moiety;    -   Hphob₂ is an independently selected hydrophobic moiety        comprising 6 to 30 carbons;    -   X₁ is an anionic counterion or absent;    -   b is the number of (R₁—N—[(R₂)(R₃)(Hphob₂)]) linked to the node        structure, Z, each via an    -   L₂, and is from zero to 10;    -   L₃ is an independently selected linking group which links Z to        cationic group —R₄—N—[(R₅)(R₆)(R₇)];    -   R₄ is an independently selected linear or branched alkylene        (—CH— to —C₆H₁₂—) or monohydroxylalkylene (—CH(OH)— to        —C₆(OH)H₁₁(OH)—);    -   R₅, R₆, R₇ are each an independently selected alkyl or alkenyl        group containing 1 to 4 carbons (CH₃ to C₄H₉);    -   X₂ is a anionic counterion or absent;    -   c is the number of (R₄—N—[(R₅)(R₆)(R₇)]) linked to the node        structure, Z, each via an L₃, and is from zero to 10;    -   wherein the sum of a and b is from 1 to 10 inclusive;    -   the sum of b and c is from 1 to 10 inclusive; and    -   the sum of a, b, and c is from 1 to 10 inclusive.

The compositions of the present invention comprise compounds having anode structure comprising at least three contiguous glyceryl remnantunits. By “glyceryl remnant unit,” it is meant glycerol units excludingnucleophilic groups such as hydroxyl groups. Glyceryl remnant unitsgenerally may be represented as C₃H₅O for linear and dendritic remnants(Rokicki et al. Green Chemistry., 2005, 7, 52). Suitable glycerylremnant units are dehydrated forms (i.e. one mole of water removed) ofthe following glyceryl units: linear-1,4 (L_(1,4)) glyceryl units;linear-1,3 (L_(1,3)) glyceryl repeat units; dendritic (D) glycerylunits; terminal-1,2 (T_(1,2)) units; and terminal-1,3 (T_(1,3)) units.Examples of such glyceryl remnant repeat and terminal units are shownbelow (to the right side of the arrows). The corresponding glyceryl unit(shown to the left side of arrows; includes hydroxyls) are shown aswell:

linear-1,4 (L_(1,4)) glyceryl repeat units

linear-1,3 (L_(1,3)) glyceryl repeat units

dendritic (D) glyceryl repeat units, which lead to branched or cycliccompounds

terminal-1,2 (T_(1,2)) units

and terminal-1,3 (T_(1,3)) units

In certain embodiments, in addition to glyceryl remnant units, a nodestructure may comprise one or more additional oxyalkyl units. Theoxyalkyl units may be generically described as —(O—R)— where R=C₁-C₄linear or branched alkyl, such as —CH₂CH₂—, —CH(CH₃)CH₂—, and—CH₂CH₂CH₂—, that originate from reacting optional co-monomers such asas 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, ethylene carbonate,1,2 propylene carbonate, and 1,3 propylene carbonate. For example, ageneral formula of glyceryl remnant unit and adjacent oxyalkyl unit maybe illustrated as:

and, as further example, a polyglyceryl-co-1,3-propanediol andaccordingly have the node structure:

As will be recognized by those of skill in the art, due to the nature ofthe polymerization of the compounds of the present invention and thenomenclature adopted herein, in certain embodiments, a node of thepresent invention may further include a terminal (with respect to thenode itself) three carbon alkyl group. For example, shown below is anexample node of the present invention derived from glycerol wherein uponpolymerization the node structure forms seven glyceryl remnant unitswith one terminal three carbon alkyl group labeled as C₃H₅ remnantbelow:

Those skilled in the art of polymer chemistry will recognize that apolyglycerol, like any typical polymer, is comprised of repeating unitsand end groups. In the simple case of a polymer formed by condensationof monomer units (elimination of water during polymerization), the endgroups are comprised of the parent molecule while the repeating unit isderived from the parent monomer minus a water molecule. Such is the casefor linear polyglycerols, which can be synthesized by using the monomerglycerol.

The polymerization of glycerol is illustrated in the figure below, wherew moles of glycerol are polymerized to form a linear polyglycerol with(1-w) repeating units and 1 end group. For clarification, the end groupis demarcated by hashed lines. Note that the repeating unit formula(C₃H₆O₂) is equal to the glycerol unit formula (C₃H₈O₃) minus water(H₂O). Also note that the sum of the end group units [(C₃H₇O₂) plus(OH)] equals the formula of glycerol (C₃H₈O₃) and that (1-w) moles ofwater are formed as a by-product of polymerization.

Furthermore, if this principle is carried onto the description of thedehydrated polyether (glyceryl remnant), one would find that theglyceryl repeating unit remnant would have the formula (C₃H₅O). Notably,the terminal remnant would have the formula (C₃H₅)

This is further illustrated in the structure below, where repeating unitisomers have been demarcated by parentheses (7 total repeat units) andthe terminal glyceryl remnant demarcated by brackets (1 terminalglyceryl remnant), yielding a total DP of 8.

In addition to C₃H₅ terminal remnant units and C₃H₅O remnant repeatunits, there may also be C₃H₅O₂ remnant units and C₃H₅O terminal remnantunits present when the molecule is contains certain isomers containingdendritic-based cyclic units. This is illustrated below, where repeatand terminal units are demarcated by parentheses for a pentaglycerolwhich contains two dendritic-based cyclic units. Unless otherwisespecified, the repeat and terminal remnant units are of the formulaC₃H₅O.

According to certain preferred embodiments, each node structure of thepresent invention includes from three to about 20 glyceryl remnant units(and optionally one or more oxyalkyl units) and is capable of havingfrom 3 to about 21 total combined groups, selected from nucleophilicgroups, hydrophobic groups (Hphob₁), cationic groups(—R₄—N—[(R₅)(R₆)(R₇)]), cationic hydrophobic groups(—R₁—N—[(R₂)(R₃)(Hphob₂)]), and combinations of two or more thereof,either bonded thereto (for nucleophilic groups) or linked thereto vialinking groups (for hydrophobic, cationic, and/or cationic hydrophobicgroups). In certain preferred embodiments, the node structure consistsonly of carbon, hydrogen, and oxygen atoms from glyceryl remnant units.In certain preferred embodiments, the node structure consists only ofcarbon, hydrogen, and oxygen atoms from glyceryl remnant units andoxyalkyl units. In certain preferred embodiments, all glyceryl remnantunits, and optional oxylalkyl units if any, of the node structure arecontiguous. According to certain embodiments, the node structure has aratio of carbon atoms to oxygen atoms (by number) that is from about 2.5to about 4.5:1, preferably from about 2.5 to about 3.5:1, such as fromabout 2.6 to about 3.4:1, such as from about 2.8 to about 3.4:1.

Examples of suitable node structures are illustrated below in thedescription of certain specific examples of cationic polyglycerylcompounds. As one skilled in the art will readily appreciate, thepolyglyceryl node structure includes a plurality of ether functionalgroups, and as such, the compounds may further be described as“polyethers.”

As described above, the cationic polyglyceryl compounds of the presentinvention further comprise at least one cationic group and at least onehydrophobic moiety. A compound of the present invention may comprise anysuitable combination of one or more cationic groups, hydrophobic groups,and/or cationic hydrophobic groups (i.e. a cationic group wherein ahydrophobic moiety constitutes a portion of the cationic group) suchthat the compound has both at least one cationic group and at least onehydrophobic moiety. For example, in certain embodiments, a compound ofthe present invention may comprise one cationic hydrophobic group alone(or optionally in combination with any additional number of separatecationic groups, cationic hydrophobic groups, or hydrophobic groups), ormay comprise at least one cationic group (with or without hydrophobicmoieties) and at least one hydrophobic group alone (or optionally incombination with any additional number of separate cationic groups,cationic hydrophobic groups, or hydrophobic groups).

Any suitable cationic group may be linked to the node structure via alinking group in a compound of the present invention. Suitable cationicgroups may include groups bearing a positive charge, such as, forexample, an amine, including a quarternary amine or a tertiary amine (inthe latter case one of the R groups bonded to the nitrogen would be ahydrogen (H)). In a preferred embodiment, the cationic moiety is aquaternary amine. Examples of preferred quaternary amines include thoseillustrated by the structures —R₁—N—[(R₂)(R₃)(Hphob₂)] and—R₄—N—[(R₅)(R₆)(R₇)], as shown in Formula I, wherein R₁ and R₄ areindependently selected linear, branched, saturated or unsaturated C₁ toC₆ hydrocarbon chains that may be optionally further substituted withnucleophilic functional groups such as —OH, —SH or —NH₂; R₂, R₅, R₆, andR₇ are independently selected C₁ to C₄ alkyl groups (CH₃ to C₄H₉) orhydrogen (H); R₃ is an independently selected C₁ to C₄ alkyl group (CH₃to C₄H₉), hydrogen, or a hydrophobic moiety; and Hphob₂ is a hydrophobicmoiety. Examples of preferred R₁ and R₄ groups include C₁ to C₃ linearalkyl groups or 2-hydroxypropyl. In certain preferred embodiments, R₁and R₄ are CH₂CH(OH)CH₂—. Examples of preferred C₁ to C₄ alkyl groupsinclude hydrogen, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl,and isobutyl.

The relative amounts of cationic moieties and position on thepolyglyceryl compound may vary. As such, both “b” and “c” in Formula Iare each independently from zero to ten, more preferably from zero to 5,and more preferably from zero to 3, provided that the total number ofcationic moieties per node structure, i.e. the sum of b and c, is fromone to ten inclusive. In preferred embodiments, b is at least one. Incertain preferred embodiments the sum of b and c is from one to 5, morepreferably from one to 3, and more preferably from one to 2.

Serving to charge balance each cationic moiety is optional anioniccounterions X₁ and/or X₂. Anionic counterions X₁ and X₂ are independentorganic or inorganic cosmetically acceptable anions. Typical inorganicanions are halides, sulfates, phosphates, nitrates, and borates. Mostpreferred are halides, especially chloride. Another suitable organicanionic counterions include methosulfate, toluoyl sulfate, acetate,citrate, taurate, glycolate, lactate, gluconate, and benzenesulfonate,and the like.

Any suitable hydrophobic moieties (e.g. Hphob₁ and Hphob₂ in Formula I)may be incorporated in the compounds of the present invention. By“hydrophobic moiety,” it is meant a nonpolar moiety that contains atleast one of the following: (a) a carbon-carbon chain of at least sixcarbons in which none of the six carbons is a carbonyl carbon or has ahydrophilic moiety bonded directly to it; (b) three or more alkyl siloxygroups (—[Si(R)₂—O]—); and/or (c) three or more oxypropylene groups insequence. A hydrophobic moiety may be, or include, linear, cyclic,aromatic, saturated or unsaturated groups. Preferred hydrophobicmoieties include 6 or more carbon atoms, more preferably from 8 to 30carbon atoms, even more preferably from 10 to 26 carbon atoms, and mostpreferably from 12 to 24 carbon atoms. Examples of hydrophobic moietiesinclude linear or branched, saturated or unsaturated alkyl moieties,e.g. linear or branched, saturated or unsaturated C₁₀-C₃₀ alkyl, such asdecyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl (myristyl),pentadecyl, hexadecyl (cetyl, palmityl), heptadecyl, heptadecenyl,hepta-8-decenyl, hepta-8,11-decenyl, octadecyl (stearyl), nonadecyl,eicosanyl, henicosen-12-yl, henicosanyl, docosanyl (behenyl), and thelike as well as benzyl. Certain preferred hydrophobic moieties includeheptadecyl, heptadecenyl, hepta-8-decenyl, hepta-8,11-decenyl and thelike. Other examples of hydrophobic moieties include groups such aspoly(oxypropylene), poly(oxybutylene), poly(dimethylsiloxane), andfluorinated hydrocarbon groups containing a carbon chain of at least sixcarbons in which none of the six carbons has a hydrophilic moiety bondeddirectly to it, and the like. Examples of certain preferred hydrophobicmoieties for Hphob₁ are undecyl, pentadecyl heptadecenyl, andhepta-8-decenyl, and for Hphob₂ are dodecyl (lauryl), cocoalkyl, andstearyl.

The relative amounts of hydrophobic moieties and position on thepolyglyceryl compound may vary. As such, both “a” and “b” in Formula Iare each independently from zero to ten, more preferably from zero to 5and more preferably from zero to 3 provided that the total number ofhydrophobic moieties per node structure, i.e. the sum of a and b, isfrom one to ten inclusive. In preferred embodiments, b is at least one.In certain preferred embodiments the sum of a and b is from one to 5,more preferably from one to 3, and more preferably one to 2.

According to certain preferred embodiments, the compounds of the presentinvention are compounds of Formula I wherein the sum of a+b+c+d may beless than or equal to 5, or greater than 5. In such embodiments, if thesum of a+b+c+d is less than or equal to 5, then the quotient of a+b+cdivided by a+b+c+d (a+b+c/a+b+c+d) is preferably greater than 0.33.Alternatively, if the sum of a+b+c+d is greater than 5, then thequotient a+b+c/a+b+c+d is from 0.04 to 0.9. In certain more preferredembodiments, if the sum of a+b+c+d is greater than 5, then the quotienta+b+c/a+b+c+d is from 0.04 to 0.7, more preferably 0.04 to 0.6.

The compounds of the present invention may have any suitable linkinggroups (e.g. L₁, L₂, and/or L₃ in Formula I) for linking cationic groupsand/or hydrophobic groups to the node. By “linking to the node” it ismeant that the cationic group and/or hydrophobic group is bonded to thenode with only a linking group therebetween. Examples of suitablelinking groups include functional moieties that when linked to at leasttwo carbon atoms form ethers, esters, carbamates (urethanes), amides,ketones, or carbonates. That is, as will be understood by one of skillin the art, each linking group may be selected from: —O—, —OC(O)—,—OC(O)N(H)—, —C(O)N(H)—, —C(O)—, —OC(O)O—, and the like. Preferredlinking groups include ether (—O—), and ester —(OC(O)—) linkages, morepreferably ether linkages for linking groups L₂ and L₃ and ether orester linkages for linking group L₁.

In certain embodiments, the linking group that are present (e.g. L₁, L₂,and/or L₃) are wholly or partially derived from a hydroxyl group of thepolyglyceryl repeat units that were reacted in the process of making thecationic polyglyceryl compound/composition. For example, if a hydroxylgroup present on a polyglyceryl is reacted with fatty acids undercondensation reaction conditions, then the resulting node structure willbe have hydrophobic moieties covalently linked thereto by L₁ groups thatare ester functional groups (—OC(O)—). According to another embodiment,the various linking groups may be derived from a difunctional reagent.For example, if a hydroxyl group on the polyglyceryl is reacted with adiisocyanate, followed by reaction with a fatty alcohol, then theresulting Z will be substituted with hydrophobic moieties covalentlylinked to the node structure by L₁ groups that are carbamate (urethane)functional groups.

The cationic polyglyceryl compounds of the present invention may haveany suitable nucleophilic groups bonded to the node structures. Bynucleophilic groups, it is meant electron donating functional groupssuch as hydroxyl (—OH), amino (—NH₂), and thiol (—SH) groups. In apreferred embodiment each nucleophilic group is a hydroxyl group (—OH).The number of nucleophilic groups “d” directly bonded to the nodestructure is from 1 to about 21, preferably from 1 to about 16, andpreferably from 1 to about 11.

While not intending to be limiting to any of the following structures,applicants provide herein specific examples of compounds within thescope of the invention to further illustrate compounds of Formula I, andcompositions comprising such compounds. For example, in certainpreferred embodiments a composition of the present invention maycomprise a cationic polyglyceryl compoundN-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium chloride decaglycerylether, the idealized structure for which is shown below:

Wherein with reference to Formula I,

-   -   (a) Z, represented by the structure below, is a decaglyceryl        remnant comprised of glyceryl remnant units [with a C/O ratio of        30/10=3]

-   -   (b) d is the number of nucleophilic groups (—OH) directly        attached to Z and is equal to 9    -   (c) L₁ is absent    -   (d) Hphob₁ is absent    -   (e) a is 0    -   (f) L₂ is an ether linking group which links Z to R₁        -   —O—    -   (g) R₁ is 2-hydroxypropyl

-   -   (h) N is a nitrogen species;

-   -   (i) R₂ is a methyl group        -   —CH₃    -   (j) R₃ is a methyl group        -   —CH₃    -   (k) Hphob₂ is a lauryl group

-   -   (l) X₁ is the counterion        -   Cl^(⊖)    -   (m) b is 1 since there is 1 (L₂-R₁—N—[(R₂)(R₃)(Hphob₂)]) per Z    -   (n) L₃ is absent    -   (o) R₄ is absent    -   (p) R₅ is absent    -   (q) R₆ is absent    -   (r) R₇ is absent    -   (s) X₂ is absent    -   (t) c is 0 since there is 0 (L₃-R₅—N—[(R₆)(R₇)(R₈)]) per Z;    -   (u) the sum of a and b is equal to 1    -   (v) and the sum of b and c is 1    -   (w) and the sum of a, b, and c is 1.

In certain preferred embodiments a composition of the present inventionmay comprise a cationic polyglyceryl compound(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium)(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium) octaglycerylether, the idealized structure for which is shown below:

-   -   (a) Z, represented by the structure below, is a octaglyceryl        remnant comprised of glyceryl remnant units[with a C/O ratio of        22/8=2.75]

-   -   (b) d is the number of nucleophilic groups directly attached to        Z and is equal to 6    -   (c) L₁ is absent    -   (d) Hphob₁ is absent    -   (e) a is 0 since there are no PG hydroxyls substituted with        (L₁-Hphob₁)    -   (f) L₂ is an ether linking group which links Z to R₁        -   —O—    -   (g) R₁ is 2-hydroxypropyl

-   -   (h) N is a nitrogen species;

-   -   (i) R₂ is a methyl group        -   —CH₃    -   (j) R₃ is a methyl group        -   —CH₃    -   (k) Hphob₂ is a lauryl group

-   -   (l) X₁ is the counterion        -   Cl^(⊖)    -   (m) b is 1 since there is 1 (L₂-R₁—N—[(R₂)(R₃)(Hphob₂)]) per Z    -   (n) L₃ is an ether linking group which links Z to R₄        -   —O—    -   (o) R₄ is 2-hydroxypropyl

-   -   (p) R₅ is a methyl group        -   —CH₃    -   (q) R₆ is a methyl group        -   —CH₃    -   (r) R₇ is a methyl group        -   —CH₃    -   (s) X₂ is the counterion        -   Cl^(⊖)    -   (t) c is 1 since there is on average 1 (L₃-R₅—N—[(R₆)(R₇)(R₈)])        per Z    -   (u) the sum of a and b is equal to 1    -   (v) and the sum of b and c is 2    -   (w) and the sum of a, b, and c is 2.

In certain preferred embodiments a composition of the present inventionmay comprise a cationic polyglyceryl compound(N-(2-hydroxypropyl)-N,N-dimethylcocoalkyl-1-ammonium) decaglycerylmonooleate ether, the idealized structure for which is shown below:

Wherein with reference to formula I,

-   -   (a) below, is a decaglyceryl remnant 10 remnant comprised of        glyceryl remnant units[with a C/O ratio of 30/9=3.3]

-   -   (b) d is the number of nucleophilic groups directly attached to        Z and is equal to 10    -   (c) L₁ is an ester linkage

-   -   (d) Hphob₁ is 8-heptadecenyl

-   -   (e) a is 1 since there is 1 (L₁-Hphob₁) per Z    -   (f) L₂ is an ether linking group which links Z to R₁        -   —O—    -   (g) R₁ is 2-hydroxypropyl

-   -   (h) N is a nitrogen species;

-   -   (i) R₂ is a methyl group        -   —CH₃    -   (j) R₃ is a methyl group        -   —CH₃    -   (k) Hphob₂ is cocoalkyl group which is known to those familiar        in the art to be a distribution of saturated and unsaturated        C₈-C₁₈ (based on the C chain distribution of coconut fatty acids        from coconut oil)

-   -   (l) X₁ is the counterion        -   Cl^(⊖)    -   (m)_(b) is 1 since there is 1 (L₂-R₁—N—[(R₂)(R₃)(Hphob₂)]) per Z    -   (n) L₃ is absent    -   (o) R₄ is absent    -   (p) R₅ is absent    -   (q) R₆ is absent    -   (r) R₇ is absent    -   (s) X₂ is absent    -   (t) c is 0 since there is on average 0 (L₃-R₅—N—[(R₆)(R₇)(R₈)])        per Z    -   (u) the sum of a and b is equal to 2    -   (v) and the sum of b and c is 1    -   (w) and the sum of a, b, and c is 2.

In certain preferred embodiments a composition of the present inventionmay comprise a cationic polyglyceryl compound(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium)(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium) decaglycerylmonooleate ether, the idealized structure for which is shown below:

Wherein with reference to formula I,

-   -   (a) Z, represented by the structure below, is a decaglyceryl        remnant comprised of glyceryl remnant units

-   -   (b) d is the number of nucleophilic groups directly attached to        Z and is equal to 7    -   (c) L₁ is an ester linkage

-   -   (d) Hphob₁ is 8-heptadecenyl

-   -   (e) a is 1 since there is 1 (L₁-Hphob₁) per Z    -   (f) L₂ is an ether linking group which links Z to R₁        -   —O—    -   (g) R₁ is 2-hydroxypropyl

-   -   (h) N is a nitrogen species;

-   -   (i) R₂ is a methyl group        -   —CH₃    -   (j) R₃ is a methyl group        -   —CH₃    -   (k) Hphob₂ is cocoalkyl group which is known to those familiar        in the art to be a distribution of saturated and unsaturated        C₈-C₁₈

-   -   (l) X₁ is the counterion        -   Cl^(⊖)    -   (m) b is 1 since there is on average 1        (L₂-R₁—N—[(R₂)(R₃)(Hphob₂)]) per Z    -   (n) L₃ is an ether linking group which links Z to R₄        -   —O—    -   (o) R₄ is 2-hydroxypropyl

-   -   (p) R₅ is a methyl group        -   —CH₃    -   (q) R₆ is a methyl group        -   —CH₃    -   (r) R₇ is a methyl group        -   —CH₃    -   (s) X₂ is the counterion        -   Cl^(⊖)    -   (t) c is 1 since there is on average 1 (L₃-R₅—N—[(R₆)(R₇)(R₈)])        per Z    -   (u) the sum of a and b is equal to 2    -   (v) and the sum of b and c is 2    -   (w) and the sum of a, b, and c is 3.

In certain preferred embodiments a composition of the present inventionmay comprise a cationic polyglyceryl compound(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium) decaglycerylmonooleate ether, the idealized structure for which is shown below:

Wherein with reference to formula I,

-   -   (a) Z, represented by the structure below, is a decaglyceryl        remnant comprised of glyceryl remnant units[with a C/O ratio of        30/10=3]    -   (b)

-   -   (c) d is the number of nucleophilic groups directly attached to        Z and is equal to 10    -   (d) L₁ is an ester linkage

-   -   (e) Hphob₁ is 8-heptadecenyl

-   -   (f) a is 1 since there is on average 1 (L₁-Hphob₁) per Z    -   (g) L₂ is absent    -   (h) R₁ is absent    -   (i) N is a nitrogen species;

-   -   (j) R₂ is absent    -   (k) R₃ is absent    -   (l) Hphob₂ is absent    -   (m) X₁ is absent    -   (n) b is 1 since there is 1 (L₂-R₁—N—[(R₂)(R₃)(Hphob₂)]) per Z    -   (o) L₃ is an ether linking group which links Z to R₄        -   —O—    -   (p) R₄ is 2-hydroxypropyl

-   -   (q) R₅ is a methyl group        -   —CH₃    -   (r) R₆ is a methyl group        -   —CH₃    -   (s) R₇ is a methyl group        -   —CH₃    -   (t) X₂ is the counterion        -   Cl^(⊖)    -   (u) c is 1 since there is on average X (L₃-R₅—N—[(R₆)(R₇)(R₈)])        per Z    -   (v) the sum of a and b is equal to 1    -   (w) and the sum of b and c is 1    -   (x) and the sum of a, b, and c is 2.

Methods of Making Cationic Polyglyceryl Compounds and Compositions

The cationic polyglyceryl compounds and compositions of this inventionmay be synthesized by various synthetic routes including but not limitedto the reaction of nitrogen-containing compounds with polyglycerol (PG)or polyglyceryl esters (PGE). The PG or PGE may be any of variouscommercially available varieties. Illustrative examples of PG and PGEstarting materials include but are not limited to polyglycerols (such asNatrulon® H-10 from Lonza PLC of Basel, Switzerland) and polyglycerylesters (such as Polyaldo® 10-1-O KFG and Polyaldo® 10-1-L from LonzaPLC) and polyglyceryl ethers (such as Polyglycerin Ether ML10 fromDaicel Chemical Industries, LTD. of Hiroshima, Japan)

A schematic example of a polyglycerol having 11 glyceryl repeat units(DP_(OH)=11), having L_(1,3), L_(1,4), D, T_(1,3), and T_(1,2)structural units is shown below. The three carbons which comprise eachclass of structural unit have been labeled to provide a detailedexample.

The nitrogen containing reactants may be quaternized either before orafter conjugation to the PG/PGE. Illustrative cationization reagentsinclude epoxy and halohydrin derivatives containing an amine group.Generalized structures of suitable quaternized starting reagents areshown below:

Commercially available halohydrins include Quab® 188, 342, 360, and 426which correspond to 3-chloro-2-hydroxypropyl-alkyl-dimethylammoniumchloride (CHADAC) where the alkyl groups are respectively methyl,lauryl, cocoalkyl, and stearyl. A commercially available epoxy reagentincludes Quab® 151 (2,3-epoxypropyltrimethylammonium chloride). Quab®halohydrins are commercially available from SKW QUAB Chemicals, Inc ofTheodore, Ala.

The Quab® quaternized halohydrin may be reacted with PG or PGEs in thepresence of a base catalyst. Accordingly, in one embodiment, the methodof making the C-PG includes the reaction of a PG with a quaternizedhalohydrin in the presence of a base catalyst. Suitable catalystsinclude alkali metal, particularly sodium or potassium, bases, e.g.hydroxides, particularly NaOH or KOH, carbonates, particularly K₂CO₃ orNa₂CO₃, bicarbonates, particularly KHCO₃ or NaHCO₃ and tertiary amines,particularly tertiary amines including at least one tertiary nitrogenatom in a ring system, such as 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),1,4-diazabicyclo[2.2.2]octane (DABCO), 4-(dimethylamino)pyridine (DMAP),7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), quinuclidine,pyrrocoline, and similar materials

In a preferred embodiment, an alkali metal hydroxide is utilized as abase catalyst. Suitable alkali metal hydroxides include sodiumhydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide,cesium hydroxide, lithium hydroxide, rubidium hydroxide, and strontiumhydroxide. Sodium, potassium, and calcium hydroxide are preferred due tothe lower cost and availability. Typically, the molar ratio ofhalohydrin to alkali metal hydroxide is 1:0.5 to 1:50, typically 1:1 to1:4, though more usually from 1:1 to 1:3, desirably 1:1.03 to 1:2 andparticularly from 1:1.03 to 1:1.5. The desired molar ratio of halohydrinto alkali metal hydroxide may be increased or decreased depending on theconcentration of water in solution. Typically, the molar ratio ofepoxide to alkali metal hydroxide is 1:0.01 to 1:50, typically 1:0.01 to1:10, though more usually from 1:0.01 to 1:3, desirably 1:0.01 to 1:2and particularly from 1:0.01 to 1:1.

In addition to the compounds of the invention, typical synthesisreactions may generate by-products such as2,3-propanediol-trialkylammonium chloride which is produced from theside reaction of water and the corresponding3-chloro-2-hydroxytrialkylammonium chloride or hydrolysis of2,3-epoxypropyltrimethylammonium chloride. Generally, a minimum amountof water is required for the cationization reaction to proceed. However,increasing the water content above this amount may lead to an increasein side products. However, those skilled in the art will note thatreaction conditions which minimize side products should be employed.While removal is not critical, the diol side products may be removed viaany of a variety of conventional separation processes including, forexample, precipitation, column chromatography, and solvent extraction.

Alternatively, C-PGs can be formed by reacting PGs or PGEs withhalohydrin alcohols (i.e. 3-chloro-2-hydroxypropanediol) under acidicconditions to produce a halohydrin PG/PGE intermediate. Subsequently,the product is reacted with an alkali metal hydroxide to yield aglycidyl PG/PGE which may be further reacted with an aminoalkyl ammoniumor alkyl amine to yield a C-PG. If an alkyl amine is employed, anadditional quaternization step (i.e. reaction with halomethane) may beemployed to yield the desired quaternary amine.

Alternatively, C-PGs can be formed by reacting PGs or PGEs withepichlorohydrins under basic conditions to produce an epoxy-functionalPG/PGE. Subseqently, the epoxy-functional PG/PGE may be reacted with atertiary amine to yield the desired C-PG. If a secondary amine isemployed in place of the tertiary amine, an addition quaternization step(i.e. reaction with iodomethane) may be employed to yield a quaternaryamine.

In addition, adjuvants may be used during different synthetic steps.Typical adjuvants include but are not limited to: base neutralizers suchas citric, acetic, tartaric, hydrochloric, and sulfuric acids.

The synthetic reactions will be generally be carried out in a batchmode, typically by mixing the reagents in a suitable vessel and allowingthem to react, usually under stirring for a suitable time. Fresh reagentand/or catalyst may be added occasionally, at multiple intervals orcontinuously during the reaction (semi-batch operation). It is alsopossible to use continuous or semicontinuous reaction modes if desired.

As the PGs or PGEs is modified with cationization reactants, thesolubility of the product may change based on thehydrophilicity/hydrophobicity of the cationization reactant. Thus, theintermediates and the products may have a distinct phase nature from thestarting reaction mixture. Reaction between components (generally) indifferent phases will be slower than when they are in one phase. Thedegree of compatibility of the intermediates may influence the relativespeed of reaction and thus influence the distribution of cationicfunctionalization among PG/PGEs. In some cases, a single phase liquidsystem will not form, giving rise to two different reaction products(one from each phase) that may be separated and utilized accordingly. Inthese cases, the reaction parameters may be adjusted accordingly tofavor the formation of the desired product and minimize formation of theaccompanying by product. For example, in a two-phase reaction productresulting from the reaction of CHADAC with PG-10, one phase may comprisea C-PG with a high degree of alkyl dimethylammonium functionalization,whereas the second phase may comprise a C-PG with a low degree of alkyldimethylammonium functionalization. The two phases may be separated andcollected via any of a variety of conventional separation processesincluding, for example, decanting, fractionation, centrifugation, and/orsolvent extraction.

Typically, the reactions to make the compounds of the invention can becarried out without the need for a solvent or diluent, particularly asthis will avoid any problem in isolating the desired product. However,if desired, the physical immiscibility of the starting materials may beavoided by the use of suitable inert reaction medium, solvent ordiluent; however, the reaction is preferably conducted in the bulk orwater.

Suitable solvents are liquids which remain thermally stable throughoutthe course of the reaction. Suitable examples of solvents/diluentsinclude water, and polar aprotic solvents.

Solvent and/or diluent may be included with the resulting cationicpolyglyceryl composition, either by leaving reaction solvent/diluent inthe product or by subsequent addition, to reduce product viscosity fortransport, storage and/or subsequent use. Typically suchsolvents/diluents will be used in amounts to give formulations havingfrom 50 to 90, more usually 60 to 80 and particularly about 70%, byweight of the product.

A heating step during the reaction may be employed. During this step thetemperature may be room temperature to superambient, such as from 25° C.to at least 150° C. and more usually at least 40° C. up to 90° C., withthe range 65 to 85° C. being generally suitable.

Typically, the reagents used to make the compounds of the inventionremain liquids of low vapor pressure at reaction temperatures, so thereaction can be conveniently carried out at ambient pressure thoughmoderately superambient pressure may be used if desired. It is unlikelythat it will be desirable to use subambient pressure, but by choosingsuitable involatile reagents it may be possible to carry the reactionout at moderately subambient pressure.

In certain reaction steps it may be preferred to apply subambientpressure (i.e. vacuum) to drive the reaction to completion and to removevolatile side products. It may also be preferential to apply subambientpressure to the reactants prior to the reaction for degassing purposes.

To help avoid excessive color generation, the synthesis reactions willusually be carried out in a largely oxygen free atmosphere, e.g. in anitrogen atmosphere (e.g., using a nitrogen blanket or sparge). Otherinert gases may be utilized such as argon. For larger scale production,nitrogen blanketing may be less necessary and perhaps omitted.

Another way of reducing product color is to include particulate carbon,particularly so-called “activated carbon”, or a bleaching earth, e.g.diatomaceous earth, in the reaction to absorb colored side products.When used, the amount of carbon will typically be from 0.5 to 2.5 weight% of the total reagents. Of course, this carbon or bleaching earth willgenerally be removed e.g. by filtration, before the products areincluded in end use formulations. Activated carbon and a reducing agentmay be used together in the reaction if desired. Further colorimprovement can be achieved by treatment of the reaction product withparticulate carbon, particularly activated carbon, or bleaching earth,typically at from 0.5 to 2.5 weight % of the product.

According to certain embodiments of the invention, cationic polyglycerylcompositions are used in personal care compositions. The personal carecomposition may comprise, consist of, or consist essentially of a baseand the cationic polyglyceryl composition. The base comprises water,surfactant, and optionally, any of various ingredients typically used inpersonal care products.

Any amounts of cationic polyglyceryl composition suitable to provide an“effective managing amount” where this term herein means an amount ofcationic polyglyceryl composition to provide a composition with personalcare utility. The effective managing amount typically ranges from 0.005to about 10 weight percent, and more preferably from about 0.01 to 7weight percent, and most preferably from about 0.05 to 5 weight percent.

According to certain embodiments of the invention, the cationicpolyglyceryl composition is used in amount suitable to provide enhancedhumectancy, enhanced conditioning or anti-fizz properties, enhanced foamproperties, enhanced viscosity, enhanced, and or combinations thereof.

According to certain embodiments of the invention the cationicpolyglyceryl composition is used in amount suitable to provide enhancedfoam properties. For example, the cationic polyglyceryl composition maybe included in an amount sufficient such that when the personal carecomposition is tested according to the Foam Test as described below, thepersonal care composition has a Foam Volume_(max) of at least about 10mL, preferably at least about 100 mL, more preferably at least about 200mL, more preferably at least about 300 mL, more preferably at leastabout 500 mL, and most preferably at least about 700 mL. According toother embodiments, the cationic polyglyceryl composition may be includedin an amount sufficient such that when the personal care composition istested according to the Foam Test as described below, the personal carecomposition has a % foam retention of at least about 50%, preferably atleast about 75%, more preferable at least about 90%.

According to certain embodiments of the invention the cationicpolyglyceryl composition is used in amount suitable to provide enhancedviscosity. For example, the cationic polyglyceryl composition may beincluded in an amount sufficient such that when the personal carecomposition is tested according to the Zero Shear Viscosity Test asdescribed below, the personal care composition has a Relative Viscosityof at least about 1.5, more preferably at least about 2, more preferablyat least about 3, more preferably at least about 5, more preferably atleast about 10. In certain preferred embodiments, the personal carecompositions of the present invention comprise a sufficient amount ofcationic polyglyceryl composition to achieve a Relative Viscosity of atleast about 2, preferably about 5, more preferably about 10.

According to certain embodiments of the invention the cationicpolyglyceryl composition is used in an amount suitable to provideenhanced conditioning and/or anti-fizz properties. For example, thecationic polyglyceryl composition may be included in an amountsufficient such that when the personal care composition is testedaccording to the Conditioning Test as described below, the personal carecomposition has an Average Comb Force of less than about 170 grams-force(gf), preferably less than about 165 gf, more preferably less than about160 gf. In certain preferred embodiments, the personal care compositionsof the present invention comprise a sufficient amount of cationicpolyglyceryl composition to achieve a Average Comb Force of less thanabout 170 gf, preferably less than about 165 gf, more preferably lessthan about 160 gf, and are substantially free of other known humectants.

According to other embodiments, the cationic polyglyceryl compositionmay be included in an amount sufficient such that when the personal carecomposition is tested according to the Anti-Frizz Test as describedbelow, the personal care composition has a % Frizz of less than about20%, preferably less than about 15%, more preferably less than about12%. In certain preferred embodiments, the personal care compositions ofthe present invention comprise a sufficient amount of cationicpolyglyceryl composition to achieve a % Frizz of less than about 20%,preferably less than about 15%, more preferably less than about 12, andare substantially free of other known humectants.

According to certain embodiments of the invention the cationicpolyglyceryl composition is used in amount suitable to provide enhancedhumectancy. For example, the cationic polyglyceryl composition may beincluded in an amount sufficient such that when the sample compositionis tested according to the Water Sorption Test as described below, thecationic polyglyceryl composition has a % ΔMass_(50 RH sorp) of greaterthan about 8, preferably greater than about 8.5, more preferably greaterthan about 10, even more preferably greater than about 12. In certainpreferred embodiments, the personal care compositions of the presentinvention comprise a sufficient amount of cationic polyglycerylcomposition to achieve a % ΔMass_(50 RH sorp) of greater than about 8,preferably greater than about 8.5, more preferably greater than about10, even more preferably greater than about 12, and are substantiallyfree of other known humectants.

In certain embodiments, the compositions useful in the present inventionmay include any variety of additional surfactants. The surfactants maybe anionic, zwitterionic (i.e. amphoteric or betaine), nonionic, orcationic, examples of which are detailed below. Where applicable,chemicals are specified according to their International Nomenclature ofCosmetic Ingredients (INCI) names.

According to certain embodiments, suitable anionic surfactants includethose selected from the following classes of surfactants: alkylsulfates, alkyl ether sulfates, alkyl monoglyceryl ether sulfates, alkylsulfonates, alkylaryl sulfonates, alkyl sulfosuccinates, alkyl ethersulfosuccinates, alkyl sulfosuccinamates, alkyl amidosulfosuccinates,alkyl carboxylates, alkyl amidoethercarboxylates, alkyl succinates,fatty acyl sarcosinates, fatty acyl amino acids, fatty acyl taurates,fatty alkyl sulfoacetates, alkyl phosphates, and mixtures of two or morethereof. Examples of certain preferred anionic surfactants include:

Alkyl Sulfates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumLauryl Sulfate (R=C₁₂ alkyl, M⁺=Na⁺), Ammonium Lauryl Sulfate (R=C₁₂alkyl, M⁺=NH₃ ⁺), and Sodium Coco-Sulfate (R=coconut alkyl, M⁺=Na⁺);

Alkyl Ether Sulfates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-12, and M⁺=monovalent cation. Examples includeSodium Laureth Sulfate (R=C₁₂ alkyl, M⁺=Na⁺, n=1-3), Ammonium LaurethSulfate (R=C₁₂ alkyl, M⁺=NH₃ ⁺, n=1-3), and Sodium Trideceth Sulfate(R═C₁₋₃ alkyl, M⁺=Na⁺, n=1-4);

Alkyl Monoglyceride Sulfates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumCocomonoglyceride Sulfate (RCO=coco acyl, M⁺=Na⁺) and AmmoniumCocomonoglyceride Sulfate (RCO=coco acyl, M⁺=NH₃ ⁺);

Alkyl Carboxylates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumLaurate (R=C₁₁H₂₃, M⁺=Na⁺) and Potassium Myristate (R=C₁₋₁₃H₂₇, M⁺=10;

Alkyl Ether Carboxylates

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-20, and M⁺=monovalent cation. Examples includeSodium Laureth-13 Carboxylate (R═C₁₋₂ alkyl, M⁺=Na⁺, n=13), and SodiumLaureth-3 Carboxylate (R=C₁₂ alkyl, M⁺=Na⁺, n=3);Alpha olefin sulfonates prepared by sulfonation of long chain alphaolefins. Alpha olefin sulfonates consist of mixtures of alkenesulfonates,

where R=C₈-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation, andhydroxyalkyl sulfonates,

where R=C₄-C₁₈ alkyl or mixtures thereof and M⁺=monovalent cation.Examples include Sodium C12-14 Olefin Sulfonate (R=C₈-C₁₀ alkyl, M⁺=Na⁺)and Sodium C14-16 Olefin Sulfonate (R=C₁₀-C₁₂ alkyl, M⁺=Na⁺);

Alkyl Sulfonates:

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumC13-17 Alkane Sulfonate (R=C₁₃-C₁₇ alkyl, M⁺=Na⁺) and Sodium C14-17Alkyl Sec Sulfonate (R=C₁₄-C₁₇ alkyl, M⁺=Na⁺);

Alkylaryl Sulfonates

where R=C₆-C₁₋₈ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation. Examples include SodiumDeceylbenzenesulfonate (R=C₁₀ alkyl, M⁺=Na⁺) and AmmoniumDodecylbenzensulfonate (R=C₁₂ alkyl, M⁺=NH₃ ⁺);

Alkyl Glyceryl Ether Sulfonates:

where R=C₈-C₂₄ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Sodium CocoglycerylEther Sulfonate (R=coco alkyl, M⁺=Na⁺);

Alkyl Sulfosuccinates

Where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Disodium LaurylSulfosuccinate (R=lauryl, M⁺=Na⁺).

Alkyl Ether Sulfosuccinates

Where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, n=1-12, and M⁺=monovalent cation, such as DisodiumLaureth Sulfosuccinate (R=lauryl, n=1-4, and M⁺=Na⁺)

Dialkyl Sulfosuccinates

Where R=C₆-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Diethylhexyl SodiumSulfosuccinate (R=2-ethylhexyl, M⁺=Na⁺).

Alkylamidoalkyl Sulfosuccinates

Where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=C₂-C₄ alkyl (linear or branched), and M⁺=monovalentcation, such as Disodium Cocamido MIPA-Sulfosuccinate (RCO=coco acyl,R′=isopropyl, M⁺=Na⁺).

Alkyl Sulfosuccinamates

Where R=C₈-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Disodium StearylSulfosuccinamate (R=stearyl, C₁₈H₃₇, M⁺=Na⁺).

α-Sulfo Fatty Acid Esters

Where R=C₆-C₁₆ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=C₁-C₄ alkyl, and M⁺=monovalent cation, such asSodium Methyl 2-Sulfolaurate (R=C₁₀H₂₁, R′=methyl, CH₃, and M⁺=Na⁺).

α-Sulfo Fatty Acid Salts

Where R=C₆-C₁₆ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Disodium 2-Sulfolaurate(R=C₁₀H₂₁, M⁺=Na⁺).

Alkyl Sulfoacetates

Where R=C₈-C₁₈ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Sodium LaurylSulfoacetate (R=lauryl, C₁₂H₂₅, M⁺=Na⁺).

Acyl Isethionates

Where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as SodiumCocoyl Isethionate (RCO=coco acyl, R′=H, M⁺=Na⁺) and Sodium LauroylMethyl Isethionate (RCO=lauroyl, R′=CH₃, M⁺=Na⁺).

Acyl Lactylates

Where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, M⁺=monovalent cation, such as Sodium Lauroyl Lactylate(RCO=lauroyl, M⁺=Na⁺).

Acyl Glycinates and Acyl Sarcosinates

Where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H (glycinate) or CH₃ (sarcosinate), M⁺=monovalentcation, such as Sodium Cocoyl Glycinate (RCO=coco acyl, R′=H, M⁺=Na⁺),Ammonium Cocoyl Sarcosinate (RCO=coco acyl, R′=CH₃, M⁺=NH₄ ⁺) and SodiumLauroyl Sarcosinate (RCO=lauroyl, R′=CH₃, M⁺=Na⁺).

Acyl Glutamates

Where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as DisodiumCocoyl Glutamate (RCO=coco acyl, R′=H, M⁺=Na⁺) and Disodium LauroylGlutamate (RCO=lauroyl, R′=H, M⁺=Na⁺).

Acyl Aspartates

Where RCO=C₈-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as DisodiumN-Lauroyl Aspartate (RCO=lauroyl, R′=H, M⁺=Na⁺).

Acyl Taurates

Where RCO=C₆-C₂₀ acyl (linear or branched, saturated or unsaturated) ormixtures thereof, R′=H or CH₃, M⁺=monovalent cation, such as DisodiumCocoyl Glutamate (RCO=coco acyl, R′=H, M⁺=Na⁺) and Disodium LauroylGlutamate (RCO=lauroyl, R′=H, M⁺=Na⁺).

Alkyl Phosphates

Where R=C₆-C₂₀ alkyl (linear or branched, saturated or unsaturated) ormixtures thereof and M⁺=monovalent cation, such as Potassium LaurylPhosphate (R=lauryl, C₁₂H₂₅, M⁺=K⁺) and Potassium C12-13 Alkyl Phosphate(R=C₁₂-C₁₃ alkyl, M⁺=K⁺)

Anionic derivatives of alkyl polyglucosides (APGs), including: SodiumLauryl Glucoside Carboxylate, Disodium Coco-Glucoside Citrate, SodiumCoco-Glucoside Tartrate, Disodium Coco-Glucoside Sulfosuccinate, SodiumCocoglucosides Hydroxypropylsulfonate, Sodium DecylglucosidesHydroxypropylsulfonate, Sodium Laurylglucosides Hydroxypropylsulfonate,Sodium Hydroxypropylsulfonate Cocoglucoside Crosspolymer, SodiumHydroxypropylsulfonate Decylglucoside Crosspolymer, SodiumHydroxypropylsulfonate Laurylglucoside Crosspolymer; and anionicpolymeric APG derivatives, such as those described in O'Lenick, U.S.Pat. Nos. 7,507,399; 7,375,064; and 7,335,627, and combinations of twoor more thereof, and the like.

Any of a variety of amphoteric surfactants are suitable for use in thepresent invention. As used herein, the term “amphoteric” shall mean: 1)molecules that contain both acidic and basic sites such as, for example,an amino acid containing both amino (basic) and acid (e.g., carboxylicacid, acidic) functional groups; or 2) zwitterionic molecules whichpossess both positive and negative charges within the same molecule. Thecharges of the latter may be either dependent on or independent of thepH of the composition. Examples of zwitterionic materials include, butare not limited to, alkyl betaines and alkylamidoalkyl betaines. Theamphoteric surfactants are disclosed herein with a counterion. Oneskilled in the art would readily recognize that under the pH conditionsof the compositions of the present invention, the amphoteric surfactantsare either electrically neutral by virtue of having balancing positiveand negative charges, or they have counter ions such as alkali metal,alkaline earth, or ammonium counter ions. Examples of amphotericsurfactants suitable for use in the present invention include, but arenot limited to, amphocarboxylates such as alkylamphoacetates (mono ordi); alkyl betaines; alkylamidoalkyl betaines; alkylamidoalkylsultaines; alkylamphophosphates; phosphorylated imidazolines such asphosphobetaines and pyrophosphobetaines; carboxyalkyl alkyl polyamines;alkylimino-dipropionates; alkylamphoglycinates (mono or di);alkylamphoproprionates (mono or di),); N-alkyl β-aminoproprionic acids;alkylpolyamino carboxylates; and mixtures thereof. Specific examplesinclude:

Alkyl Betaines

where R=C₈-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof.Examples include Coco-Betaine (R=coco alkyl), Lauryl Betaine (R=lauryl,C₁₂H₂₅), and Oleyl Betaine (R=oleyl, C₁₈H₃₅).

Alkyl Hydroxysultaines

where R=C₈-C₂₄ alkyl (saturated or unsaturated) or mixture thereof.Examples include Coco-Hydroxysultaine (R=coco alkyl) and LaurylHydroxysultaine (R=lauryl, C₁₂H₂₅).

Alkyl Sultaines

where R=C₈-C₂₄ alkyl (saturated or unsaturated) or mixture thereof.Examples include Lauryl Sultaine (R=lauryl, C₁₂H₂₅) and Coco-Sultaine(R=coco alkyl).

Alkylamidoalkyl Betaines

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andx=1-4. Examples include Cocamidoethyl Betaine (RCO=coco acyl, x=2),Cocamidopropyl Betaine (RCO=coco acyl, x=3), Lauramidopropyl Betaine(RCO=lauroyl, and x=3), Myristamidopropyl Betaine (RCO=myristoyl, andx=3), Soyamidopropyl Betaine (R=soy acyl, x=3), and OleamidopropylBetaine (RCO=oleoyl, and x=3).

Alkylamidoalkyl Hydroxysultaines

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include Cocamidopropyl Hydroxysultaine (RCO=coco acyl, x=3),Lauramidopropyl Hydroxysultaine (RCO=lauroyl, and x=3),Myristamidopropyl Hydroxysultaine (RCO=myristoyl, and x=3), andOleamidopropyl Hydroxysultaine (RCO=oleoyl, and x=3).

Alkylamidoalkyl Sultaines

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof.Examples include Cocamidopropyl Sultaine (RCO=coco acyl, x=3),Lauramidopropyl Sultaine (RCO=lauroyl, and x=3), MyristamidopropylSultaine (RCO=myristoyl, and x=3), Soyamidopropyl Betaine (RCO=soy acyl,x=3), and Oleamidopropyl Betaine (RCO=oleoyl, and x=3).

Alkyl Phosphobetaines

where R=C₆-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as Sodium Coco PG-Dimonium ChloridePhosphate, where R=coco alkyl and M⁺=Na⁺.

Phospholipids

where R=C₆-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof,x=1-3 or mixtures thereof, x+y=3, z=x, a=0 to 2, B=O⁻ or OM, A=Anion,and M=Cation (refer to U.S. Pat. Nos. 5,215,976; 5,286,719; 5,648,348;and 5,650,402), such as Sodium Coco PG-Dimonium Chloride Phosphate,where R=coco alkyl, x=2, B=O⁻, y=1, z=1, A=Cl⁻, a=1, and M=Na⁺.

Phospholipids

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof,n=1-4, x=1-3 or mixtures thereof, x+y=3, z=x, a=0 to 2, B=O⁻ or OM,A=anion, and M=cation (refer to U.S. Pat. Nos. 5,215,976; 5,286,719;5,648,348; and 5,650,402). Examples include Cocamidopropyl PG-DimoniumChloride Phosphate (RCO=coco acyl, n=3, x=3, z=3, A=Cl⁻, B and M areabsent, y=0, and a=0) and Myristamidopropyl PG-Dimonium ChloridePhosphate (RCO=myristoyl, n=3, x=3, z=3, A=Cl⁻, B and M are absent, y=0,and a=0).

Alkyl Amphoacetates

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Sodium Lauroamphoacetate(RCO=lauroyl and M⁺=Na⁺) and Sodium Cocoamphoacetate (RCO=coco acyl andM⁺=Na⁺).

Alkyl Amphodiacetates

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Disodium Lauroamphodiacetate(RCO=lauroyl and M=Na⁺) and Disodium Cocoamphodiacetate (RCO=coco acyland M=Na⁺).

Alkyl Amphopropionates

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Sodium Lauroamphopropionate(RCO=lauroyl and M⁺=Na⁺) and Sodium Cocoamphopropionate (RCO=coco acyland M⁺=Na⁺).

Alkyl Amphodipropionates

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation. Examples include Disodium Lauroamphodipropionate(RCO=lauroyl and M⁺=Na⁺) and Disodium Cocoamphodipropionate (RCO=cocoacyl and M⁺=Na⁺).

Alkyl Amphohydroxypropylsulfonates

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as Sodium Lauroamphohydroxypropylsulfonate(RCO=lauroyl and M⁺=Na⁺) and Sodium Cocoamphohydroxypropylsulfonate(RCO=coco acyl and M⁺=Na⁺).

Alkyl Amphohydroxyalkylphosphates

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andM⁺=monovalent cation, such as Sodium Lauroampho PG-Acetate Phosphate(RCO=lauroyl and M⁺=Na⁺).

Alkyl Amine Oxides

where R=C₆-C₂₄ alkyl (saturated or unsaturated) or mixtures thereof.Examples include Cocamine Oxide (R=coco alkyl) and Lauramine Oxide(RCO=lauryl).

Alkylamidoalkyl Amine Oxides

where RCO=C₆-C₂₄ acyl (saturated or unsaturated) or mixtures thereof andx=1-4. Examples include Cocamidopropylamine Oxide (RCO=coco acyl, x=3)and Lauramidopropylamine Oxide (RCO=lauroyl, x=3), and combinations oftwo or more thereof, and the like.

Any of a variety of ethoxylated nonionic surfactants are suitable foruse in the present invention. Examples of suitable nonionic surfactantsinclude, but are not limited to: fatty alcohol, fatty acid, or fattyamide ethoxylates; monoglyceride ethoxylates; sorbitan esterethoxylates; mixtures thereof; and the like. Certain preferredethoxylated nonionic surfactants include polyethyleneoxy derivatives ofpolyol esters, wherein the polyethyleneoxy derivative of polyol ester(1) is derived from (a) a fatty acid containing from about 8 to about22, and preferably from about 10 to about 14 carbon atoms, and (b) apolyol selected from sorbitol, sorbitan, glucose, α-methyl glucoside,polyglucose having an average of about 1 to about 3 glucose residues permolecule, glycerol, pentaerythritol and mixtures thereof, (2) containsan average of from about 10 to about 120, and preferably about 20 toabout 80 ethyleneoxy units; and (3) has an average of about 1 to about 3fatty acid residues per mole of polyethyleneoxy derivative of polyolester. Examples of such preferred polyethyleneoxy derivatives of polyolesters include, but are not limited to PEG-80 Sorbitan Laurate andPolysorbate 20.

While the compositions may comprise ethoxylated materials as describedabove in accord with certain embodiments, according to certain otherembodiments, the compositions of the present invention are substantiallyfree of ethoxylated materials. As used herein, the term “substantiallyfree of ethoxylated materials” means a composition that comprises lessthan 1% by weight of total ethoxylated materials. In preferredembodiments, compositions that are substantially free of ethoxylatedmaterials comprise less than 0.5%, more preferably less than 0.1%, andeven more preferable are free of, ethoxylated materials.

As used herein, the term “ethoxylated material” means a materialcomprising one or more moieties derived from or prepared by thering-opening oligomerization or polymerization of ethylene oxide andcomprising one or more oxyethylene (—CH₂CH₂O—) moieties. Examples ofethoxylated materials include, but are not limited to, ethoxylatedsurfactants, emulsifiers, solubilizers, rheology modifiers, conditioningagents, preservatives, and the like, such as, for example anionicsurfactants: polyoxyethylene alkyl ether sulfates (a.k.a. alkyl ethersulfates), polyoxyethylene alkyl ether carboxylates (a.k.a. alkyl ethercarboxylates), polyoxyethylene alkyl ether sulfosuccinate esters;nonionic surfactants, emulsifiers, and solubilizers: polyoxyethylenealkyl ethers and esters, polysorbates, ethoxylated sorbitan fatty acidesters, ethoxylated glyceryl fatty acid esters, poloxamers; rheologymodifiers: polyoxyethylene esters (e.g. PEG-150 Distearate),ethyoxylated alkyl glucoside esters (e.g. PEG-120 Methyl GlucoseTrioleate), acrylic copolymers with ethoxylated associativemacromonomers (e.g. Acrylates/Steareth-20 Methacrylate Copolymer),ethoxylated cellulose ethers (e.g. Hydroxyethylcellulose); conditioningagents: ethoxylated polyquaterniums (e.g. Polyquaternium-10); and thelike.

Any of a variety of non-ethoxylated nonionic surfactants are alsosuitable for use in the present invention. Examples of suitablenon-ethoxylated nonionic surfactants include alkyl polyglucosides, alkylpolypentosides, polyglyceryl esters, polyglyceryl ethers, polyglycerylsorbitan fatty acid esters, sucrose esters, and sorbitan esters, andcombinations of two or more thereof and the like. Certain preferrednon-ethoxylated nonionic surfactants include C₈-C₁₈ polyglycerylmonoesters (e.g. polyglyceryl-4 caprylate/caprate, polyglyceryl-10caprylate/caprate, polyglyceryl-4 caprate, polyglyceryl-10 caprate,polyglyceryl-4 laurate, polyglyceryl-5 laurate, polyglyceryl-6 laurate,polyglyceryl-10 laurate, polyglyceryl-10 cocoate, polyglyceryl-10myristate, polyglyceryl-10 oleate, polyglyceryl-10 stearate, andcombinations of two or more thereof) and c₈-c₁₈ polyglyceryl monoethers(e.g. polyglyceryl-4 lauryl ether, polyglyceryl-10 lauryl ether.

Another class of suitable nonionic surfactants includes long chain alkylglucosides or polyglucosides, which are the condensation products of (a)a long chain alcohol containing from about 6 to about 22, and preferablyfrom about 8 to about 14 carbon atoms, with (b) glucose or aglucose-containing polymer. Preferred alkyl glucosides comprise fromabout 1 to about 6 glucose residues per molecule of alkyl glucoside. Apreferred glucoside is Decyl Glucoside, which is the condensationproduct of decyl alcohol with a glucose polymer and is availablecommercially from Cognis Corporation of Ambler, Pa. under the tradename, “Plantaren 2000N UP.” Other examples include Coco-Glucoside andLauryl Glucoside.

The compositions of the present invention may comprise any of a varietyof additional other ingredients used conventionally inhealthcare/personal care compositions (“personal care components”).These other ingredients nonexclusively include one or more, pearlescentor opacifying agents, thickening agents, emollients, secondaryconditioners, humectants, chelating agents, actives, exfoliants, andadditives which enhance the appearance, feel and fragrance of thecompositions, such as colorants, fragrances, preservatives, pH adjustingagents, and the like.

Compositions useful in the present invention may also include any of avariety of conventional thickening agents. Examples of such thickeningagents include: electrolytes (e.g. Sodium Chloride, Ammonium Chloride,Magnesium Chloride); naturally-derived polysaccharides (e.g. XanthanGum, Dehydroxanthan Gum, Cyamopsis Tetragonoloba (Guar) Gum, Cassia Gum,Chondrus Crispus (Carrageenan) Gum, Alginic Acid and alginate gums(Algin, Calcium Alginate, etc.), Gellan Gum, Pectin, MicrocrystallineCellulose); derivatives of natural polysaccharides (e.g.Hydroxyethylcellulose, Ethyl Hydroxyethylcellulose, CetylHydroxyethylcellulose, Methylcellulose, Hydroxypropylcellulose, SodiumCarboxymethylcellulose, Hydroxypropyl Methylcellulose, HydroxypropylGuar, Carboxymethyl Hydroxypropyl Guar, C18-22 HydroxylalkylHydroxypropyl Guar); alkali-swellable emulsion (ASE) polymers (e.g.Acrylates Copolymer, available under the trade name Carbopol® AQUA

SF-1 from Noveon Consumer Specialties, Brecksville, Ohio, and AcrylatesCopolymer available under the trade name Aculyn™ 33 from Dow PersonalCare, Spring House, Pa.); hydrophobically-modified alkali-swellableemulsion (HASE) polymers (e.g. Acrylates/Steareth-20 MethacrylateCopolymer, Acrylates/Steareth-20 Methacrylate Crosspolymer, andAcrylates/Ceteth-20 Itaconate Copolymer); hydrophobically-modifiedacid-swellable emulsion polymers (e.g. Acrylates/Aminoacrylates/C10-30Alkyl PEG-20 Itaconate Copolymer and Polyacrylate-1 Crosspolymer);hydrophobically-modified acrylate crosspolymers, such as AcrylatesC10-30 Alkyl Acrylates Crosspolymer, available under the trade nameCarbopol® 1382 from Lubrizol Corp., Brecksville, Ohio; and hydrophobicnon-ethoxylated micellar thickeners (e.g. Glyceryl Oleate, CocamideMIPA, Lauryl Lactyl Lactate, or Sorbitan Sesquicaprylate).

Any of a variety of skin and/or hair conditioning agents in addition tothe cationic polyglyceryl compositions are suitable for use in thisinvention. Examples include: cationic surfactants (e.g. CetrimoniumChloride, Stearamidopropyl Dimethylamine, Distearyldimonium Chloride,Lauryl Methyl Gluceth-10 Hydroxypropyldimonium Chloride); cationicpolymers (e.g. cationically-modified polysaccharides, includingPolyquaternium-10, Polyquaternium-24, Polyquaternium-67, StarchHydroxypropyltrimonium Chloride, Guar Hydroxypropyltrimonium Chloride,and Hydroxypropyl Guar Hydroxypropyltrimonium Chloride, and cationicpolymers derived from the (co)polymerization ofethylenically-unsaturated cationic monomers with optional hydrophilicmonomers, including Polyquaternium-5, Polyquaternium-6,Polyquaternium-7, Polyquaternium-11, Polyquaternium-14,Polyquaternium-15, Polyquaternium-28, Polyquaternium-39,Polyquaternium-44; Polyquaternium-76); silicones and siliconederivatives (e.g. Dimethicone and derivatives thereof, such as alkyl-,polyalkyloxy-, cationically-, anionically-modified dimethicone(co)polymers); and emollients (e.g. Caprylic/Capric Triglycerides,Mineral Oil, Petrolatum, Di-PPG-2 Myreth-10 Adipate).

Any of a variety of humectants in addition to the cationic polyglycerylcompositions, which are capable of providing moisturization andconditioning properties to the personal cleansing composition, aresuitable for use in the present invention. Examples of suitablehumectants nonexclusively include polyols, such as Glycerin, PropyleneGlycol, 1,3-Propanediol, Butylene Glycol, Hexylene Glycol, polyglycerins(e.g. Polyglycerin-3, Polyglyceryn-6, Polyglycerin-10), polyethyleneglycols (PEGs), and polyoxyethylene ethers of α-methyl glucose, such asMethyl Gluceth-10 and Methyl Gluceth-20.

Examples of suitable chelating agents include those which are capable ofprotecting and preserving the compositions of this invention.Preferably, the chelating agent is ethylenediamine tetraacetic acid(“EDTA”), and more preferably is Tetrasodium EDTA or TetrasodiumGlutamate Diacetate.

Suitable preservatives include, for example, organic acids, parabens(e.g. Methylparaben, Ethylparaben, Propylparaben, Butylparaben,Isobutylparaben), quaternary ammonium species (e.g. Quaternium-15),phenoxyethanol, DMDM hydantoin, Diazolidinyl Urea, Imidazolidinyl Urea,Iodopropynyl Butylcarbamate, Methylisothazolinone,Methylchloroisothizaolinone, Benzyl Alcohol, Caprylyl Glycol, DecyleneGlycol, Ethylhexylglycerin, and Gluconolactone. Preferred are organicacid preservatives that comprise at least one carboxylic acid moiety andare capable of preserving a composition of the present invention againstmicrobial contamination Examples of suitable organic acids includeBenzoic Acid and alkali metal and ammonium salts thereof (e.g. SodiumBenzoate and the like), Sorbic Acid and alkali metal and ammonium saltsthereof (e.g. Potassium Sorbate and the like), p-Anisic Acid and alkalimetal and ammonium salts thereof, Salicylic Acid and alkali metal andammonium salts thereof, and the like. In certain preferred embodiments,the organic acid preservative comprises Benzoic Acid/Sodium Benzoate,Sorbic Acid/Potassium Sorbate, or combinations thereof.

The pH of the composition may be adjusted to the appropriate value usingany number of cosmetically acceptable pH adjusters, including: alkalimetal and ammonium hydroxides (e.g. Sodium Hydroxide, PotassiumHydroxide), alkali metal and ammonium carbonates (e.g. PotassiumCarbonate), organic acids (e.g. Citric Acid, Acetic Acid, Glycolic Acid,Lactic Acid, Malic acid, Tartaric Acid), and inorganic acids (e.g.Hydrochloric Acid, Phosphoric Acid), and the like. In certain preferredembodiments, the pH is adjusted to be from 3 to 10, in certain morepreferred embodiments, from 5 to 9, including from 6 to 8. In certainpreferred embodiments, the electrolyte concentration of the compositionis less than 10% by weight, more preferably less than 5%, morepreferably less than 2%.

The cationic polyglyceryl compositions, optional surfactants andoptional other components of the composition may be combined accordingto the present invention via any conventional methods of combining twoor more fluids or solids. For example, one or more compositionscomprising, consisting essentially of, or consisting of at least onecationic polyglyceryl compositions and one or more compositionscomprising, consisting essentially of, or consisting of water,surfactants or suitable ingredients may be combined by pouring, mixing,adding dropwise, pipetting, pumping, and the like, one of thecompositions comprising the cationic polyglyceryl compositions into orwith the other in any order using any conventional equipment such as amechanically stirred propeller, paddle, and the like.

The methods of the present invention may further comprise any of avariety of steps for mixing or introducing one or more of the optionalcomponents described hereinabove with or into a composition comprising acationic polyglyceryl compositions either before, after, orsimultaneously with the combining step described above. While in certainembodiments, the order of mixing is not critical, it is preferable, inother embodiments, to pre-blend certain components, such as thefragrance and the nonionic surfactant before adding such components intoa composition comprising the cationic polyglyceryl compositions.

The compositions useful in the present invention involve formulationssuitable for administering to the target tissues, such as mammalian skinsuch as human skin. In one embodiment, the composition comprises acationic polyglyceryl compositions and a base, preferably acosmetically-acceptable base. As used herein, the term“cosmetically-acceptable base” means a base that is suitable for use incontact with the skin without undue toxicity, incompatibility,instability, irritation, allergic response, and the like. This term isnot intended to limit the base for use solely as a cosmetic (e.g., theingredient/product can be used as a pharmaceutical).

The compositions may be made into a wide variety of product types thatinclude but are not limited to cleansing liquid washes, gels, sticks,sprays, solid bars, shampoos, pastes, foams, powders, mousses, shavingcreams, wipes, patches, wound dressing and adhesive bandages, hydrogels,films and make-up such as foundations, mascaras, and lipsticks. Theseproduct types may comprise several types of cosmetically-acceptablecarriers including, but not limited to solutions, emulsions (includingmicroemulsions and nanoemulsions), suspensions, gels, and solids. Thefollowing are non-limitative examples of such carriers. Other carrierscan be formulated by those of ordinary skill in the art.

The compositions of the present invention may comprise water. In certainpreferred embodiments, the composition comprises greater than 60%, morepreferably from 70-95% water.

The compositions useful in the present invention can be formulated assolutions. Solutions typically include an aqueous or organic solvent(e.g., from about 50% to about 99.99% or from about 90% to about 99% ofa cosmetically acceptable aqueous or organic solvent). Examples ofsuitable organic solvents include: polyglycerols, propylene glycol,polyethylene glycol (200, 600), polypropylene glycol (425, 2025),glycerol, 1,2,4-butanetriol, sorbitol esters, 1,2,6-hexanetriol,ethanol, and mixtures thereof. In certain preferred embodiments, thecompositions of the present invention are aqueous solutions comprisingfrom about 50% to about 99% by weight of water.

According to certain embodiments, compositions useful in the subjectinvention may be formulated as a solution comprising an emollient. Suchcompositions preferably contain from about 2% to about 50% of anemollient(s). As used herein, “emollients” refer to materials used forthe prevention or relief of dryness, as well as for the protection ofthe skin. A wide variety of suitable emollients are known and may beused herein. A lotion can be made from such a solution. Lotionstypically comprise from about 1% to about 20% (e.g., from about 5% toabout 10%) of an emollient(s) and from about 50% to about 90% (e.g.,from about 60% to about 80%) of water.

The compositions of this invention can also be formulated as a gel(e.g., an aqueous, alcohol, alcohol/water, or oil gel using a suitablegelling agent(s)). Suitable gelling agents for aqueous and/or alcoholicgels include, but are not limited to, natural gums, acrylic acid andacrylate polymers and copolymers, and cellulose derivatives (e.g.,hydroxymethyl cellulose and hydroxypropyl cellulose). Suitable gellingagents for oils (such as mineral oil) include, but are not limited to,hydrogenated butylene/ethylene/styrene copolymer and hydrogenatedethylene/propylene/styrene copolymer. Such gels typically comprisesbetween about 0.1% and 5%, by weight, of such gelling agents.

The present compositions may be of varying phase compositions, but arepreferably aqueous solutions or otherwise include an exterior aqueousphase (e.g., aqueous phase is the most exterior phase of thecomposition). As such, compositions of the present invention may beformulated to be oil-in-water emulsions that are shelf-stable in thatthe emulsion does not lose phase stability or “break” when kept atstandard conditions (22 degrees Celsius, 50% relative humidity) for aweek or more after it is made.

In certain embodiments, the compositions produced via the presentinvention are preferably used as or in healthcare products for treatingor cleansing at least a portion of a mammalian body, for example, thehuman body. Examples of certain preferred personal care products includevarious products suitable for application to the skin, hair, oral and/orperineal region of the body, such as shampoos, hand, face, and/or bodywashes, bath additives, gels, lotions, creams, and the like. Asdiscussed above, applicants have discovered unexpectedly that theinstant methods provide personal care products having reduced irritationto the skin and/or eyes and, in certain embodiments one or more ofdesirable properties such as flash foaming characteristics, rheology,and functionality, even at high surfactant concentrations. Such productsmay further include a substrate onto which a composition is applied foruse on the body. Examples of suitable substrates include a wipe, pouf,sponge, and the like as well as absorbent articles, such as a bandage,sanitary napkin, tampon, and the like.

The present invention provides methods of treating and/or cleansing thehuman body comprising contacting at least a portion of the body with acomposition of the present invention. Certain preferred methodscomprising contacting mammalian skin, hair and/or vaginal region with acomposition of the present invention to cleanse such region and/or treatsuch region for any of a variety of conditions including, but notlimited to, acne, wrinkles, dermatitis, dryness, muscle pain, itch, andthe like. In certain preferred embodiments, the contacting stepcomprises applying a composition of the present invention to human skin,hair or vaginal region. The cleansing methods of the present inventionmay further comprise any of a variety of additional, optional stepsassociated conventionally with cleansing hair and skin including, forexample, lathering, rinsing steps, and the like.

EXAMPLES

The following test methods and procedures were used:

Degree of Reaction Conversion of Polyglyceryl or Polyglyceryl Ester with3-chloro-2-hydroxypropyldimethylalkylammonium chloride (CHADAC):

In the following description, chlorine refers to all Cl species (as bothfree ions and covalently bound). As seen in the scheme below, the CHADACreagent contains covalently bound chlorine. Covalently bound chlorinerefers to Cl species covalently bonded to the 2-hydroxypropyl species ofCHADAC reagents and is referred to as Cl_(b). The CHADAC reagent alsocontains a chloride counterion, referred to as Cl_(c). During thereaction, the CHADAC reagent is consumed and yields an additional moleof Cl_(c). Reaction conversion was determined by measuring the change inCl_(c) concentration.

In the following description Cl_(a) refers to the sum of bound chlorine(Cl_(b)) and chloride counterion (Cl_(c)) species. Below, the subscriptst=0 and t=f (with respect to Cl_(a),Cl_(b) and Cl_(c)) refer to theinitial starting time and final time after the reaction.

The percent conversion of the reaction was determined by the followingequation:

${\% \mspace{14mu} {Conversion}} = {\left( {1 - \frac{{mol}\mspace{14mu} {Cl}_{b,{t = f}}}{{mol}\mspace{14mu} {Cl}_{b,{t = 0}}}} \right) \times 100}$

Where the mol Cl_(b,f) and mol Cl_(b,f) may be determined by

${{mol}\mspace{14mu} {Cl}_{b,{t = 0}}} = \frac{g\mspace{14mu} {CHADAC} \times {wt}\mspace{14mu} \% \mspace{14mu} {Cl}_{b,{t = 0}}}{{MW}_{Cl}}$${{mol}\mspace{14mu} {Cl}_{b,{t = f}}} = \frac{g\mspace{14mu} {Reaction} \times {wt}\mspace{14mu} \% \mspace{14mu} {Cl}_{b,{t = f}}}{{MW}_{Cl}}$

where the g CHADAC refers to the mass of CHADAC reagent utilized in thereaction, g Reaction refers to the total mass of the reaction, andMW_(Cl) refers to the molecular weight of chlorine. The wt % Cl_(b,t=0)and wt % Cl_(b,t=f) are determined by the equations

wt % Cl_(b,t=0)=wt % Cl_(a,t=0)−wt % Cl_(c,t=0),

wt % Cl_(b,t=f)=wt % Cl_(a,t=f)−wt % Cl_(c,t=f)

where the wt % Cl_(a,t=0),wt % Cl_(c,t=0),wt % Cl_(a,t=f),wt %Cl_(c,t=f) are measured directly by titration.

Titration experiments were conducted as follows: on a suitable balance,the reaction product was accurately weighed, transferred into a 500 mLErlenmeyer flask, and subsequently dispersed or dissolved in 10 mL of1.5% hydrogen peroxide solution. Approximately 40 mL of isopropanol wasadded and mixed followed by the addition of approximately 0.5 mL of0.13% diphenylcarbazone in ethanol solution. The resulting solution wasthen titrated with previously standardized 0.003 M mercuric acetatevolumetric solution loaded in a microburet to a pink endpoint. Ifnecessary the endpoint of a blank solution was determined. The wt %Cl_(c) is determined by

${\% \mspace{14mu} {Cl}_{c}} = \frac{\left( {V_{Spl} - B} \right) \times K_{Cl} \times 100}{{Wt}_{sample}}$

where Wt_(sample) is the weight of the sample in μg, V_(spl) is thesample titration volume in mL, B is the blank titration volume in mL,and K_(Cl) is the equivalency factor of mercuric acetate volumetricsolution in μg/mL.

Foam Test:

The following Foam Test was performed on various test compositions todetermine the foam volume upon agitation according to the presentinvention. First, 1.0 g of test material (e.g., polyglycerylcomposition), on an active basis, is added to a beaker. Then 500 g of a0.72 g/L calcium chloride solution was added to the beaker, anddeionized water was added to bring the final mass to 1000 g. As such atest composition was formed with 0.1% active polyglyceryl composition(or comparative composition) in simulated hard water. To determine thefoam volume, the test composition (1000 mL) was added to a sample tankof a SITA R-2000 foam tester (commercially available from Future DigitalScientific, Co.; Bethpage, N.Y.). The test parameters were set to repeatthree runs (series count=3) of 250 ml sample size (fill volume=250 ml)with thirteen stir cycles (stir count=13) for a 15 second stir time percycle (stir time=15 seconds) with the rotor spinning at 1200 RPM(revolution=1200) at a temperature setting of 30° C.±2° C. Foam volumedata was collected at the end of each stir cycle and the average andstandard deviations for the three runs was determined. The foam volumeafter the thirteenth stir cycle is recorded as the maximum foam volume,Foam Volume_(max). The volume of foam 18 minutes after the FoamVolume_(max) has been achieved is recorded as Foam Volume=_(t=18 min).The % foam volume retention is then determined by the following equation

${\% \mspace{14mu} {Foam}\mspace{14mu} {Volume}\mspace{14mu} {Retention}} = {100 \times \frac{{Foam}\mspace{14mu} {Volume}_{t = {18\mspace{14mu} \min}}}{{Foam}\mspace{14mu} {Volume}_{\max}}}$

Zero Shear Viscosity Test:

The following Zero Shear Viscosity Test was performed on variouspersonal care compositions to determine the viscosity according to thepresent invention. Viscosities of test formulations were conducted at25° C. using a controlled-stress rheometer (AR-2000, TA InstrumentsLtd., New Castle, Del., USA). Steady-state shear stress sweeps wereperformed at 25.0±0.1° C. using a double-wall Couette geometry. Dataacquisition and analysis were performed with the Rheology Advantagesoftware v4.1.10 (TA Instruments Ltd., New Castle, Del., USA).Zero-shear apparent viscosities for samples that demonstrated Newtonianbehavior are reported as the average of viscosity values obtained over arange of shear stresses (i.e. 0.1-100 dynes/cm²). For pseudoplastic(shear-thinning) fluids, zero-shear apparent viscosities (η₀) werecalculated via the fitting of shear stress sweep data to an Ellis orCarreau viscosity model.

The Relative Viscosity, η_(relative) was determined by the followingequation,

$\eta_{relative} = \frac{\eta_{0\mspace{14mu} {Example}}}{\eta_{0\mspace{14mu} {Base}}}$

where η_(0 example) is the zero shear viscosity of a formula with aninventive or comparative material and η_(0 base) is the zero shearviscosity of the “base formula,” i.e., without the particular testcomposition. Thus η_(relative) is a measure of how well a particulartest composition (e.g., cationic polyglyceryl composition) increasesviscosity of the base formula. The error associated with zero shearviscosity measurements in accord with this procedure is less than 5%.

Conditioning Test:

The following Conditioning Test was performed by applying a personalcare test composition to hair and evaluating for wet feel based oncombing. Instron mechanical combing tests developed at Textile ResearchInstitute (TRI, Princeton, N.J.) were utilized to evaluate theseproperties. The tested formulas were applied to 6 inch virgin mediumbrown tresses which had been bleached for 40 minutes at 40° C. using 6%H₂O₂. The procedure was as follows: dry hair tresses were treated underflowing water for 30 seconds. Excess water was removed from each tresswith a squeegee motion using the fingers. The tress was wet again for anadditional 30 seconds, squeegeed once, then 0.3 mL of personal care testcomposition was applied and lathered into the tress for 30 seconds.After lathering, the tress was combed with a coarse-toothed comb toremove tangles and then with a second comb similar to the comb mountedon the Instron tensile tester. Standard wet tress combing was run on theInstron tensile tester, Instron 1122 with 5500R electronics andsoftware. The tress was then smoothed between the fingers and mounted inthe grips of the Instron. The combing was repeated 5 times, smoothingthe tress after each pass. After five passes the tress was removed fromthe grips and rinsed under flowing water to yield a cumulative rinsetime of 15, 30, and 60 seconds. The average load after a 60 secondcumulative rinse time is reported as the “Average Comb Force” with unitsof grams force (gf). The average load was determined by measuring theforce exerted through the first through fourth inch of the tress duringthe second and third comb stroke. If the maximum load (268 gf) of theinstrument was reached before the comb passed through the fourth inch ofthe tress, the instrument did not record an average load and a value of268 gf was assigned. The number of tangle events was determined from theaverage number of strokes that reached a max force of 268 gf during the0 to 6th inch of combing the tress. The “% of tangled strokes” weretaken as the number of tangle events which occurred during strokes 1-4taken from 0, 15, 30, and 60 cumulative rinse times divided by thenumber of total strokes. The fifth combing step was not used in dataanalysis due to the significant amount of work previously conducted onthe hair with comb steps 1-4.

Water Sorption Test:

The following Water Sorption Test was performed using the technique ofdynamic vapor sorption (DVS). For each test composition, samples wereplaced in sample pans and inserted into a DVS Intrinsic Instrument(available from Surface Measurement Systems of Allentown, Pa.) andallowed to equilibrate at 25° C., 20% relative humidity (RH) until thetarget dm/dt (change in mass/change in time) equilibration parameter of0.001% was reached. The humidity was increased in 10% RH increments upto 90% RH, and then increased to 98% RH as the maximum humidity step.Following the RH ramp, the humidity was decreased from 98% RH to 90% RH,followed by a decrease in RH by 10% increments until 20% RH was reached.RH steps were programmed to occur once equilibration was obtained(0.001% dm/dt) or after 240 min if equilibration was not obtained withinthe timeframe. Measurements were taken every five seconds during theentire duration of the experiment.

The % change in mass at 50% RH was measured as both a sorption anddesorption process. During the sorption process, the % change in mass (%ΔMass_(50 RH sorp)) is calculated using the following equation,

${\% \mspace{14mu} \Delta \; {Mass}_{50\mspace{14mu} {RH}\mspace{14mu} {sorp}}} = {\frac{{Wt}_{20->{50\mspace{14mu} {RH}}} - {Wt}_{ref}}{{Wt}_{ref}} \times 100}$

where the Wt_(20→50RH), refers to the equilibrium (or pseudoequilibrium)weight of the sample at 50% RH as the chamber humidity was increasedfrom 20 to 50% RH. Wt_(ref) refers to the equilibrium weight of thesample at 20% RH after being placed in the chamber from atmosphericconditions. The average value of % ΔMass_(50 RH sorp) for three samplesis reported.

Similarly, the % change in mass during the desorption process (%ΔMass_(50 RH desorp)) was calculated using the following equation,

${\% \mspace{14mu} \Delta \; {Mass}_{50\mspace{14mu} {RH}\mspace{14mu} {desorp}}} = {\frac{{Wt}_{98->{50\mspace{14mu} {RH}}} - {Wt}_{ref}}{{Wt}_{ref}} \times 100}$

where the Wt_(98→20RH), refers to the equilibrium (or pseudoequilibrium)weight of the sample at 50% RH as the chamber humidity was decreasedfrom 98 to 50% RH. The Wt_(ref) again refers to the equilibrium weightof the sample at 20% RH after being placed in the chamber fromatmospheric conditions.

Those skilled in the art will recognize that sorption versus desorptionvalues can be different based on the ability of the humectant to retainvs absorb water. Moisture retention of a humectant delivered from awater-based system may be more accurately gauged by the desorptionequilibrium values, whereas moisture uptake is more accurately gauged bythe sorption equilibrium values.

Anti-Frizz Test:

The following Anti-Frizz Test was performed. Mulatto Blended hair wasacquired from International Hair Importers (IHI) and was supplied inrounded tresses of approximately 4 g weight (not including the epoxyplug) and straightened length of approximately 220 mm (not including theepoxy plug). Hair was pre-washed by IHI using a simple surfactantsolution (no fragrance, color or other additives), and pre-combed at TRIto a common level of alignment prior to straightening. Prior totreatment with a personal care test composition, the 4 g mulatto hairtress was wet for 30 seconds under a shower head dispensing water at 40°C. and 1 gallon/minute. Subsequently, the personal care test compositionwas applied according to the following procedure: personal care testcomposition was added to the tress at 10% dosage based on weight oftress, massaged into the tress for 30 seconds, and rinsed for 30 secondsusing 40° C. water at a flow rate of 1 gallon/minute. After treatment,the sample was blow dried and straightened with a brush. After eachtress was thus set, it was hung in a controlled humidity chamber at 25%RH. Once all tresses were straightened, there was the need to quicklyre-set the earlier prepared tresses which had begun to undergo someslight reversion even under low humidity conditions. Once all tresseswere visually-judged to possess comparable straightness, the humiditywas then raised to 50% and the experiment was begun. Following treatmenteach tress was placed on a pre-selected position on a board in thehumidity chamber. The hair was illuminated by ambient light via a pairof vertically mounted fluorescent fixtures. Images of the hair-mountingboards with 4 tresses were collected using a 12.9 Megapixel Fuji S-5prodigital camera. Images were acquired before, immediately aftertreatment, every 15 minutes for the first hour, 30 minutes for thesubsequent 4 hours, and then every 60 minutes for the last 3 hours posttreatment. Images were saved directly to the hard-drive of a computercontrolling the camera.

The volume of individual tresses was determined using custom writtensoftware operating under Lab View™ v8.5. In the analysis, the tress wasseparated from the background by a thresholding technique. The resultingbinary image was utilized in the calculation of frizz. The percent offrizz for each tress was calculated as a percentage of reversion as afunction of time relative to the initial and final area of the tresses,

${\% \mspace{14mu} {Frizz}} = {100 \times \frac{A_{t} - A_{0}}{A}}$

where A_(t) is equal to the area of tress at a specific time, t; A₀ isequal to the initial area of the straightened tress; and A is equal tothe area of a non-straightened tress.

Example I Preparation of Inventive Cationic Polyglyceryl Compositionsand Comparative Examples

The following abbreviations are used herein: PG-10=polyglyceryl-10,PG-10-1-O=polyglyceryl-10 monooleate, PG-10-1-L=polyglyceryl-10monolaurate, PG-10-1-LE=polyglyceryl-10 lauryl ether, Quab® 342(3-chloro-2-hydroxypropyl-lauryl-dimethylammonium chloride)=LD, Quab®360 (3-chloro-2-hydroxypropyl-cocoalkyl-dimethylammonium chloride)=CD,and Quab® 188 (3-chloro-2-hydroxypropyl-trimethylammonium chloride)=TM.Polyglyceryl materials were obtained from available as Natrulon® H-10,Polyaldo® 10-1-O KFG, and Polyaldo® 10-1-L from Lonza PLC. Thepolyglyceryl material Polyglycerin Ether ML10 was obtained from DaicelChemical Industries, Ltd. All Quab® reagents were obtained from SKW QUABChemicals, Inc of Mobile, Ala.

Cationic polyglyceryl composition, Inventive Example, E1 was synthesizedas follows: to a clean, appropriately sized flask equipped with anoverhead stirrer, a heating mantle/thermocouple connected to atemperature controller and N₂ sparge tube, deoxygenated polyglycerin-10(0.120 mol, 115.16 g, 79% Active) and Quab® 360 (0.156 moles, 140.23 g,40% active) were added. The mixture was lightly sparged with nitrogengas for 10 minutes. Subsequently, the material was heated to 35° C. at arate of 5° C./min. Once at 35° C., NaOH pellets (0.174 mol, 6.96 g) wereadded over the course of several minutes while mixing. After theaddition of the NaOH pellets, the mixture was heated to 80° C. at a rateof 5° C./min. The solution was stirred at 80° C. for 5 hr after whichthe solution was allowed to come to room temperature. The cooledmaterial was discharged to an appropriate container. Note that as anoptional post-reaction step, the pH of some products was adjusted tobelow 7 via addition of acetic acid prior to being discharged.

Additional cationic polyglyceryl compositions, Inventive ExamplesE2-E16, were synthesized by varying the type or proportions of startingmaterials: polyglycerol vs polyglyceryl ester, base catalyst, CHADACreagent, and/or addition of water. The variation in starting materialsused, reaction conditions, and products are summarized in Table 1 below.When additional water was utilized it was added before sparging thepolyol and CHADAC reagents.

For E6 and E16, the CHADAC reagents were added sequentially, with TMbeing added to the initial reaction mixture and CD being added afterheating at 80° C. for 2.5 hrs. Reaction conditions and conversion datafor E1-E 16 are also shown in Table 1.

Comparative Examples, C1 and C2 compositions were synthesized in asimilar manner as E1-E16. An example of the synthesis of C1 is asfollows: to a clean, appropriately sized flask equipped with an overheadstirrer, a heating mantle/thermocouple connected to a temperaturecontroller and N₂ sparge tube, deoxygenated polyglycerol (0.160 mol,153.9 g, 79% active) and Quab® 188 (0.208 moles, 56.6 g, 69% active)were added. The mixture was lightly sparged with nitrogen gas for 10minutes. Subsequently, the material was heated to 35° C. at a rate of 5°C./min. Once at 35° C., NaOH pellets (0.234 mol, 9.35 g) were added overthe course of several minutes while mixing. After the addition of theNaOH pellets, the mixture was heated to 80° C. at a rate of 5° C./min.The solution was stirred at 80° C. for 5 hr after which the solution wasallowed to come to room temperature. As an optional step, the pH of someproducts was adjusted to below 7 with the use of acetic acid. Afterneutralization of the reaction, the material was cooled and dischargedto an appropriate container. Reaction conditions and conversion data forC1 and C2 are also shown in Table 1.

TABLE 1 Reaction conditions and conversion data for the synthesis ofcationic polyglyceryl compositions and comparative examples. Time atPolyol CHADAC Reagent Mass Moles 80° C. % Ex # Type Moles Type MolesWater (g) NaOH (hr) Conversion E1 PG-10 0.120 CD 0.156 0 0.174 5.00 102E2 PG-10 0.120 CD 0.234 0 0.268 5.25 74 E3 PG-10 0.120 LD 0.156 0 0.1828.00 105 E4 PG-10 0.470 LD 0.611 0 0.689 5.00 99 E5 PG-10 0.121 TM + LD¹TM—0.28, 0 0.460 4.75 97 LD—0.16 E6 PG-10 0.120 TM + LD² TM—0.27, 00.462 4.50 99 LD—0.15 E7 PG-10-1-L 0.124 CD 0.156 0 0.174 5.00 96 E8PG-10-1-L 0.124 LD 0.156 11.44 0.176 5.50 95 E9 PG-10-1-L 0.124 TM 0.15623.78 0.595 4.50 100 E10 PG-10-1-L 0.124 TM 0.446 0 0.463 4.50 92 E11PG-10-1-L 0.206 TM 0.467 24.52 0.488 6.00 89 E12 PG-10-1-LE 0.120 LD0.156 0 0.175 6.00 98 E13 PG-10-1-O 0.120 CD 0.156 25.86 0.176 5.00 93E14 PG-10-1-O 0.120 LD 0.156 24.84 0.175 5.50 99 E15 PG-10-1-O 0.200 TM0.277 292.49 0.288 5.00 99 E16 PG-10-1-O 0.120 TM + LD¹ TM—0.27, 24.510.467 4.75 97 LD—0.16 C1 PG-10 0.160 TM 0.208 0 0.234 4.25 101 C2 PG-100.121 TM 0.401 0 0.445 4.25 102 ¹TM and LD added simultaneously. ²TMadded first. LD added second.

Example II Foam Properties of Inventive Cationic PolyglycerylCompositions and Comparative Examples

The compositions of Example I were tested according to the Foam Test,described above. The results, including maximum foam volume (FoamVolume_(max)), foam volume_(t=18 min), and % foam volume retention aregiven in Table 2 and FIG. 3. Ingredient names of inventive examples arebased on the molar quantities of CHADAC reagents and PG/PGE reagent.With reference to FIG. 3, shown are maximum foam volume (mL) (white bar)and foam volume_(t=18 min) (black bar) of inventive and comparativeexamples in simulated hard water. The highlighted gray area indicates aportion of the graph which does not have meaningful y-axis values buthas been included to allow space for the description of structuralfeatures. Structural features of inventive and comparative examples arenoted as white horizontal bars transversing samples which contain thefeature. Cat-Hphob=(L₂-R₂—N—[(R₃)(R₄)(Hphob₂)]).Cat=(L₃-R₅—N—[(R₆)(R₇)(R₈)]). Hphob=(L₁-R₁—Hphob₁).

TABLE 2 Foam properties of Inventive Cationic Polyglyceryl Compositionsand Comparative Examples in Simulated Hard Water. Test Foam Foam % FoamMaterial/ Vol- Vol- Volume Trade- ume_(max) ume_(t=18 min) Reten- nameIngredient Name (mL) (mL) tion E1 (CD)₁ PG-10 765 733 96 E2 (CD)₂ PG-10773 747 97 E4 (LD)₁ PG-10 750 720 96 E5 (LD)₁(TM)₂ PG-10 757 706 93 E6(LD)₁(TM)₂ PG-10 754 720 95 E7 (CD)₁ PG-10-1-L 515 482 94 E8 (LD)₁PG-10-1-L 490 458 93 E9 (TM)₁ PG-10-1-L 59 37 63 E10 (TM)₃ PG-10-1-L 3514 40 E11 (TM)₂ PG-10-1-L 85 63 74 E12 (LD)₁ PG-10-1-LE 801 778 97 E13(CD)₁ PG-10-1-O 313 289 92 E14 (LD)₁ PG-10-1-O 310 283 91 E15 (TM)₁PG-10-1-O 18 0.7 4 E16 (LD)₁(TM)₂ PG-10-1-O 81 60 74 C1 (TM)₁PG-10 1.3 00 C2 (TM)₃PG-10 1.7 0 0 Natrulon PG-10 47 0 0 H-10 PG-10-1-L PG-10-1-L388 359 93 Polyaldo PG-10-1-O 42 24 57 10-1-0 KFG Glucquat Lauryl methylgluceth-10 740 462 62 125 hydroxypropyl dimonium Chloride

Also tested were the following: Comparative Example Glucquat™ 125(Lauryl Methyl Gluceth-10 Hydroxypropyldimonium Chloride, commerciallyavailable from Lubrizol Corp., Brecksville, Ohio), Comparative ExamplePolyaldo® 10-1-O (polyglyceryl-10 oleate available from Lonza GroupPLC), and Comparative Example PG-10-1-L (polyglyceryl-10 laurate, alsoavailable from Lonza Group PLC).

Example III Water Sorption Properties of Cationic PolyglycerylCompositions and Comparative Examples

Selected Inventive Examples described in Example I above, as well asGlucquat™ 125 were tested according to the Water Sorption Test, alsodescribed above. The results, including % ΔMass_(50 RH sorp), and %ΔMass_(50 RH desorp) are given in Table 3.

Table 3 shows water sorption data of comparative and inventivematerials. The % mass change upon desorption (high to low RH) indicatesthe material is able to retain water once absorbed. Conversely, the %mass change upon sorption (low to high RH) indicates the ability of thematerial to absorb water.

TABLE 3 Water Sorption of Inventive Cationic Polyglyceryl Compositionsand Comparative Examples. Test Material/ % % Tradename/ Ingredient NameΔMass_(50 RH Sorp) ΔMass_(50 RH Desorp) E4 (LD)₁ PG-10 8.9 9.7 E5(LD)₁(TM)₂ PG-10 13.1 22 Glucquat Lauryl methyl 8.1 8.2 125 gluceth-10hydroxypropyl- dimonium

Example IV Preparation of Comparative and Inventive Personal CareCompositions

Personal care formulations were prepared using selected inventiveexamples of Example I. In addition, comparative personal careformulations were prepared using Glucquat™ 125, Polyaldo® 10-1-O, aswell as no humectant. A premix comprised of quaternium-15 and a fractionof the required PEG-80 sorbitan laurate and deionized water was allowedto mix in a beaker until all the quaternium-15 had dissolved. To aseparate beaker fitted with a mechanical stirrer and hotplate, water,PEG-150 distearate, and the remaining fraction of PEG-80 sorbitanlaurate were added. This was mixed at low-medium speed and heat wasslowly applied to the batch to increase the temperature to 80° C. Themixture was heated until all material was dissolved. Approximately onehalf of the required purified water was added to the beaker and allowedto mix until the temperature reached 60° C. Sodium trideceth sulfate,cocamidopropyl betaine, and tetrasodium edta were added to the mixtureand allowed to cool to 40° C. The material was allowed to mix for 30min. The premix was combined with the surfactant solution and allowed tomix for 20 min. When the temperature reached 25° C., the pH was adjustedto 6.5. A particular commercially available humectant or experimentalmaterial was added. The pH was checked to ensure it was within tolerance(6.5±0.3). Water was added in q.s. to 100%. The compositions of thevarious comparative compositions (and active weight percentages ofingredients) are shown in the Table 4a below while inventive personalcare compositions are shown in Table 4b.

TABLE 4a Comparative Personal Care Compositions. Test Material/Tradename Ingredient Name C3 C4 C5 Control (no Control (no Humectant) —— — Humectant) Polyaldo 10-1-0 PG-10-1-O — 1.00 — KFG Glucquat 125Lauryl methyl gluceth-10 — — 1.00 hydroxypropyldimonium chloride Dowicil200 Quaternium-15 0.05 0.05 0.05 Atlas G-4280 PEG-80 Sorbitan Laurate3.60 3.60 3.60 Ethox PEG-6000 PEG-150 Distearate 0.45 0.45 0.45 DSSpecial Cedepal TD403 Sodium Trideceth Sulfate 2.70 2.70 2.70 MFLD TEGOBetain L7V Cocamidopropyl Betaine, 3.75 3.75 3.75 Versene 100 XLTetrasodium EDTA 0.10 0.10 0.10 Sodium Hydroxide Sodium Hydroxide q.s.q.s. q.s. solution (20%) Citric Acid Citric Acid q.s. q.s. q.s. solution(20%) Purified Water Water q.s. q.s. q.s.

TABLE 4b Inventive Personal Care Compositions. Test Material/ TradenameIngredient Name E17 E18 E19 E4 (LD)₁ PG-10 1.00 — — E5 (LD)₁(TM)₂ PG-10— 1.00 — E14 (LD)₁PG-10-1-O — — 1.00 Dowicil 200 Quaternium-15 0.05 0.050.05 Atlas G-4280 PEG-80 Sorbitan Laurate 3.60 3.60 3.60 Ethox PEG-6000PEG-150 Distearate 0.45 0.45 0.45 DS Special Cedepal TD403 SodiumTrideceth Sulfate 2.70 2.70 2.70 MFLD TEGO Betain L7V CocamidopropylBetaine, 3.75 3.75 3.75 Versene 100 XL Tetrasodium EDTA 0.10 0.10 0.10Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. solution (20%) CitricAcid Citric Acid q.s. q.s. q.s. solution (20%) Purified Water Water q.s.q.s. q.s.

Example V Conditioning Properties of Cationic Polyglyceryl Compositionsand Comparative Examples

The personal care compositions of Example IV were tested according tothe Conditioning Test, described above, except that 8 tresses were used(n=8) per example. The results, including are given in Table 5.Inventive examples (E17-E19) have lower percentage of tangled strokesand lower average comb force (indicating better conditioning) ascompared to Comparative Example, C3 (no humectant).

TABLE 5 Conditioning Properties of Hair Treated with ComparativeExamples and Inventive Examples. Avg Comb Force after Example # 60 secRinse (gf) % of Tangled Strokes C3 208 29 C4 141 13 C5 176 26 E17 155 19E18 141 17 E19 148 23

Example VI Anti-Frizz Properties of Cationic Polyglyceryl Compositionsand Comparative Examples

The personal care compositions of Example IV were tested according tothe Anti-Frizz Test, described above. The results, including are givenin Table 6.

TABLE 6 Anti-Frizz analysis of Hair Treated with Personal CareCompositions: Comparative Examples (C3- C5) and Inventive Examples(E17-E19) % Frizz at Example # 8 hr Std Err. (%) C3 19.94 1.13 C4 19.111.29 C5 13.65 1.04 E17 17.99 1.29 E18 10.93 0.80 E19 12.24 2.56

Example VII Preparation of Comparative and Inventive Personal CareCompositions

Personal care formulations were prepared using inventive and comparativecompositions of Example I. In addition, comparative personal careformulations were prepared using Glucquat™ 125, Polyaldo® 10-1-O,Polyaldo® 10-1-L, Natrulon® H-10, as well as no humectant.

The formulations were prepared as follows: to a beaker fitted with amechanical stirrer and hotplate, water, ammonium lauryl sulfate, andammonium laureth sulfate were added. This was mixed at low-medium speedand heat was slowly applied to the batch to increase the temperature to75° C. When the batch reached 75° C., cocamide MEA was added. Heatingwas stopped after the ingredients were completely dissolved and thebatch was allowed to cool to approx. 25° C., while mixing was continuedat medium speed. When the batch reached 25° C., sodium chloride and DMDMhydantoin were added and mix until completely dissolved. pH was adjustedto 6.4±0.2 using citric acid or sodium hydroxide solution. After the pHwas adjusted a particular commercially-available C-PG/test material wasadded. Water was added in q.s. to 100%. The composition was mixed atlow-medium speed. If the composition was hazy, it was placed in a sealedjar in an oven and heated to 50° C. until clear. The comparativecompositions (and active weight percentages of ingredients) are shown inthe Table 7a while inventive examples are shown in Table 7b-d.

Natrulon H-10 and Polyaldo® are available from Lonza Group of Allendale,N.J. Standapol® and Comperlan are available from Cognis Corp. (now BASF)of Ambler, Pa.

TABLE 7a Comparative Personal Care Compositions. Test Material/Tradename Ingredient Name C6 C7 C8 C9 C10 C11 C12 Control (no C-PG)Control (no C-PG) — — — — — — — Polyaldo 10-1-0 PG-10-1-O — 2.00 — — — —— KFG Polyaldo 10-1-L PG-10-1-L — — 2.00 — — — — KFG Natrulon H-10 PG-10— — — 2.00 — — — Glucquat 125 Lauryl methyl gluceth-10 — — — — 2.00 — —hydroxypropyldimonium C1 (TM) PG-10 — — — — — 2.00 — C2 (TM)₃ PG-10 — —— — — — 2.00 Standapol A Ammonium Lauryl Sulfate 10.92  10.92  10.92 10.92  10.92  10.92  10.92  Standapol EA-2 Ammonium Laureth Sulfate 4.394.39 4.39 4.39 4.39 4.39 4.39 Comperlan 100 Cocamide MEA 1.24 1.24 1.241.24 1.24 1.24 1.24 Sodium Chloride Sodium Chloride 0.40 0.40 0.40 0.400.40 0.40 0.40 Glydant DMDM Hydantoin 0.06 0.06 0.06 0.06 0.06 0.06 0.06Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. q.s. q.s. q.s. q.s.solution (20%) Citric Acid solution Citric Acid q.s. q.s. q.s. q.s. q.s.q.s. q.s. (20%) Puriied Water Water q.s. q.s. q.s. q.s. q.s. q.s. q.s.

TABLE 7b Inventive Personal Care Compositions. Test Material/ TradenameIngredient Name E20 E21 E22 E23 E24 E1 (CD)₁ PG-10 2.00 — — — — E2 (CD)₂PG-10 — 2.00 — — — E4 (LD)₁ PG-10 — — 2.00 — — E5 (LD)₁(TM)₂ PG-10 — — —2.00 — E6 (LD)₁(TM)₂ PG-10 — — — — 2.00 Standapol A Ammonium LaurylSulfate 10.92  10.92  10.92  10.92  10.92  Standapol EA-2 AmmoniumLaureth Sulfate 4.39 4.39 4.39 4.39 4.39 Comperlan 100 Cocamide MEA 1.241.24 1.24 1.24 1.24 Sodium Chloride Sodium Chloride 0.40 0.40 0.40 0.400.40 Glydant DMDM Hydantoin 0.06 0.06 0.06 0.06 0.06 Sodium HydroxideSodium Hydroxide q.s. q.s. q.s. q.s. q.s. solution (20%) Citric AcidCitric Acid q.s. q.s. q.s. q.s. q.s. solution (20%) Purified Water Waterq.s. q.s. q.s. q.s. q.s.

TABLE 7c Inventive Personal Care Compositions. Test Material/ TradenameIngredient Name E25 E26 E27 E28 E29 E30 E7 (CD)₁ PG-10-1-L 2.00 — — — —— E8 (LD)₁ PG-10-1-L — 2.00 — — — — E9 (TM)₁ PG-10-1-L — — 2.00 — — —E10 (TM)₃ PG-10-1-L — — — 2.00 — — E11 (TM)₂ PG-10-1-L — — — — 2.00 —E12 (LD)₁ PG-10-1-LE — — — — — 2.00 Standapol A Ammonium Lauryl Sulfate10.92  10.92  10.92  10.92  10.92  10.92  Standapol EA-2 AmmoniumLaureth Sulfate 4.39 4.39 4.39 4.39 4.39 4.39 Comperlan 100 Cocamide MEA1.24 1.24 1.24 1.24 1.24 1.24 Sodium Chloride Sodium Chloride 0.40 0.400.40 0.40 0.40 0.40 Glydant DMDM Hydantoin 0.06 0.06 0.06 0.06 0.06 0.06Sodium Hydroxide Sodium Hydroxide q.s. q.s. q.s. q.s. q.s. q.s. solution(20%) Citric Acid solution Citric Acid q.s. q.s. q.s. q.s. q.s. q.s.(20%) Purified Water Water q.s. q.s. q.s. q.s. q.s. q.s.

TABLE 7d Inventive Personal Care Compositions. Test Material/ TradenameIngredient Name E31 E32 E33 E34 E13 (CD)₁ PG-10-1-O 2.0  — — — E14 (LD)₁PG-10-1-O — 2.0  — — E15 (TM)₁ PG-10-1-O — — 2.0  — E16 (LD)₁(TM)₂ — — —2.0  PG-10-1-O Standapol A Ammonium 10.92  10.92  10.92  10.92  LaurylSulfate Standapol Ammonium 4.39 4.39 4.39 4.39 EA-2 Laureth SulfateComperlan Cocamide 1.24 1.24 1.24 1.24 100 MEA Sodium Sodium 0.40 0.400.40 0.40 Chloride Chloride Glydant DMDM 0.06 0.06 0.06 0.06 HydantoinSodium Sodium q.s. q.s. q.s. q.s. Hydroxide Hydroxide solution (20%)Citric Acid Citric Acid q.s. q.s. q.s. q.s. solution (20%) PurifiedWater Water q.s. q.s. q.s. q.s.

Example VIII Zero Shear Viscosity of Compositions and ComparativeExamples

The zero shear viscosity of comparative Examples C6-C12 and ExamplesE20-E34 were tested according to the Zero Shear Viscosity Test,described above, to determine the thickening efficiency. The results ofthese tests are shown Table 8 and FIG. 4.

TABLE 8 Zero shear viscosity (η₀) and relative viscosity (η_(relative))of comparative and inventive personal care compositions. Example η₀ (cP)Sample η_(relative) ¹ C6²  980 Control 1.0 C7  1590 PG-10-1-O 1.6 C8 530 PG-10-1-L 0.5 C9  370 PG-10 0.4 C10 60 Glucquat 125 0.06 C11 720 C1 0.7 C12 1330 C2  1.4 E20 9290 E1  9.5 E21 15500 E2  15.8 E22 10660 E4 10.9 E23 5900 E5  6.0 E24 7000 E6  7.1 E25 12010 E7  12.2 E26 10200 E8 10.4 E27 1420 E9  1.4 E28 4470 E10 4.6 E29 2780 E11 2.8 E30 2410 E12 2.5E31 12670 E13 12.9 E32 19780 E14 20.2 E33 2860 E15 2.9 E34 14800 E1615.1$\;^{1}\eta_{relative} = \frac{\eta_{0\; {Example}}}{\eta_{0\; {Base}}}$² Sample C6 is the base formula upon which η_(0Base) is determined from.

FIG. 4 depicts the η_(relative) of 2 wt % active inventive andcomparative materials in a cleansing base formulation (ComparativeExample C6). The dashed line indicates an η_(relative) of 1. Structuralfeatures of the 2 wt % additive material are noted as white horizontalbars transversing samples which contain the feature. Samples may contain0-3 structural features: Cat-Hphob=(L₂-R₂—N—[(R₃)(R₄)(Hphob₂)]),Cat=(L₃-R₅—N—[(R₆)(R₇)(R₈)]), and/or Hphob=(L₁-R₁—Hphob₁).

As can be seen in FIG. 4, cationic polyglyceryl compositions thatinclude a cationic hydrophobic group (—R₁—N—[(R₂)(R₃)(Hphob₂)]) showedthe greatest viscosity increases. This finding is particularlysurprising given that Comparative Example, C10 which included Glucquat™125, which has a cationic hydrophobic group but contains node structurehaving ethylene oxide repeat units rather than glyceryl repeat units,results in a material which significantly thins the base formula(η_(relative)=0.06).

Example IX Preparation of Comparative and Inventive Personal CareCompositions

Personal care formulations were prepared using select inventivecompositions of Example I. In addition, comparative personal careformulations were prepared using Polyaldo® 10-1-O, Polyaldo® 10-1-L, andNatrulon® H-10.

The following personal care compositions, Examples E35-E46, wereprepared. The concentrations and particular C-PG are listed in Table 9awhile comparative formulations are listed in Tables 9b and 9c.

TABLE 9a Inventive Personal Care Compositions. Test Material/ TradenameIngredient Name E35 E36 E37 E38 E39 E40 E41 E42 E43 E44 E45 E46 E1 (CD)₁PG-10 0.50 1.0  3.5  5.0  — — — — — — — E14 (LD)₁ PG-10-1-O — — — — 0.501.0  3.5  5.0  — — — — E9 (TM)₁ PG-10-1-L — — — — — — — — 0.50 1.0  3.5 5.0  Standapol A Ammonium 10.92  10.92  10.92  10.92  10.92  10.92 10.92  10.92  10.92  10.92  10.92  10.92  Lauryl Sulfate StandapolAmmonium 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39EA-2 Laureth Sulfate Comperlan 100 Cocamide MEA 1.24 1.24 1.24 1.24 1.241.24 1.24 1.24 1.24 1.24 1.24 1.24 Sodium Sodium 0.40 0.40 0.40 0.400.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Chloride Chloride Glydant DMDM0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 HydantoinSodium Sodium q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.q.s. Hydroxide Hydroxide solution (20%) Citric Acid Citric Acid q.s.q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. solution (20%)Purified Water Water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.q.s. q.s.

TABLE 9b Comparative Personal Care Compositions. Test Material/Ingredient Tradename Name C13 C14 C15 C16 C17 C18 C19 C20 C21 C22 C23C24 Natrulon H-10 PG-10 0.50 1.0  3.5  5.0  — — — — — — — Polyaldo10-1-LPG-10-1-L — — — — 0.50 1.0  3.5  5.0  Polyaldo PG-10-1-O 0.50 1.0  3.5 5.0  10-1-O Standapol A Ammonium 10.92  10.92  10.92  10.92  10.92 10.92  10.92  10.92  10.92  10.92  10.92  10.92  Lauryl SulfateStandapol Ammonium 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.39 4.394.39 4.39 EA-2 Laureth Sulfate Comperlan 100 Cocamide MEA 1.24 1.24 1.241.24 1.24 1.24 1.24 1.24 1.24 1.24 1.24 1.24 Sodium Sodium 0.40 0.400.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Chloride ChlorideGlydant DMDM 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06 0.06Hydantoin Sodium Sodium q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.q.s. q.s. q.s. Hydroxide Hydroxide solution (20%) Citric Acid CitricAcid q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.solution (20%) Purified Water Water q.s. q.s. q.s. q.s. q.s. q.s. q.s.q.s. q.s. q.s. q.s. q.s.

TABLE 9c Comparative Personal Care Compositions. Test Material/Tradename Ingredient Name C25 C26 C27 C28 Glucquat Lauryl methylgluceth-10 0.50 1.0 3.5 5.0 125 hydroxypropyldimonium Standapol AmmoniumLauryl 10.92 10.92 10.92 10.92 A Sulfate Standapol Ammonium Laureth 4.394.39 4.39 4.39 EA-2 Sulfate Comperlan Cocamide MEA 1.24 1.24 1.24 1.24100 Sodium Sodium Chloride 0.40 0.40 0.40 0.40 Chloride Glydant DMDMHydantoin 0.06 0.06 0.06 0.06 Sodium Sodium Hydroxide q.s. q.s. q.s.q.s. Hydroxide solution (20%) Citric Acid Citric Acid q.s. q.s. q.s.q.s. solution (20%) Purified Water q.s. q.s. q.s. q.s. Water

The results are shown in FIG. 1 and Table 10. With the exception of E42,formulas containing inventive examples resulted in a thickened formula(η_(relative)>1). As seen in FIG. 1, formulations including E14 [LD)₁PG-10-1-O (closed triangles)] and E1[(CD)₁ PG-10 (closed squares)] havea maximum effect on viscosity between 2.0-3.5 wt %. Both of theseexamples contain cationic-hydrophobes. Conversely, inventive examplescontaining a hydrophobic group (Hphob₁) and a cationic group(—R₄—N—[(R₅)(R₆)(R₇)]) [(TM)₁ PG-10-1-L, E9 (formulas represented byclosed circles)] exhibit a slight increase in viscosity from doses of0.5-2.0 wt % and a more significant increase as the dose is raised to5.0 wt %.

The comparative examples containing Glucquat™ 125 (open diamonds), PG-10(open squares), and PG-10-1-L (open circles) resulted in a thinnedmaterial (η_(relative)<1) with the exception of C17 (0.5 wt %PG-10-1-L). Thus, the only comparative other than C17 capable ofthickening was PG-10-1-O (open triangles)

TABLE 10 Zero shear viscosity (η₀) and relative viscosity (η_(relative))of inventive personal care compositions and comparative personal carecompositions Example Ingredient Name η₀ (cP) Wt % Active η_(relative) ¹E35 (CD)₁ PG-10 2480 0.5 2.5 E36 (CD)₁ PG-10 3090 1.0 3.2 E37 (CD)₁PG-10 18500 3.5 18.9 E38 (CD)₁ PG-10 4360 5.0 4.4 E39 (LD)₁ PG-10-1-O2770 0.5 2.8 E40 (LD)₁ PG-10-1-O 4420 1.0 4.5 E41 (LD)₁ PG-10-1-O 33803.5 3.4 E42 (LD)₁ PG-10-1-O 620 5.0 0.6 E43 (TM)₁ PG-10-1-L 1400 0.5 1.4E44 (TM)₁ PG-10-1-L 1320 1.0 1.3 E45 (TM)₁ PG-10-1-L 2830 3.5 2.9 E46(TM)₁ PG-10-1-L 4600 5.0 4.7 C13 PG-10 750 0.5 0.8 C14 PG-10 450 1 0.5C15 PG-10 90 3.5 <0.1 C16 PG-10 60 5 <0.1 C17 PG-10-1-L 1190 0.5 1.2 C18PG-10-1-L 670 1 0.7 C19 PG-10-1-L 650 3.5 0.7 C20 PG-10-1-L 740 5 0.8C21 PG-10-1-O 1360 0.5 1.4 C22 PG-10-1-O 1370 1 1.4 C23 PG-10-1-O 27103.5 2.8 C24 PG-10-1-O 5040 5 5.1 C25 Glucquat 125 260 0.5 0.3 C26Glucquat 125 130 1 0.1 C27 Glucquat 125 38 3.5 <0.1 C28 Glucquat 125 355 <0.1

1. A compound of Formula I:

wherein, Z is a polyglyceryl node structure that comprises at least 3contiguous glyceryl remnant units; Nu are independently selectednucleophilic groups which are directly linked to Z; d is the number ofnucleophilic groups directly bonded to Z, and is from 2 to 21; L₁ is anindependently selected linking group which links Z to Hphob₁ Hphob₁ isan independently selected hydrophobic moiety comprising 6 to 30 carbons;a is the number of Hphob₁ linked to the node structure Z, each via anL₁, and is from zero to 10; L₂ is an independently selected linkinggroup which links Z to a cationic group —R₁—N—[(R₂)(R₃)(Hphob₂)]; R₁ isan independently selected linear or branched alkylene (—CH— to —C₆-H₁₂—)or monohydroxyalkylene (—CH(OH)— to —C₆-H₁₁(OH)—); N is a nitrogen atom;R₂ is an independently selected alkyl or group containing 1 to 4 carbons(CH₃ to C₄H₉) or a hydrogen atom; R₃ is an independently selected alkylgroup containing 1 to 4 carbons (CH₃ to C₄H₉) or a hydrogen atom, or anindependently selected hydrophobic moiety; Hphob₂ is an independentlyselected hydrophobic moiety comprising 6 to 30 carbons; X₁ is an anioniccounterion or absent; b is the number of (R₁—N—[(R₂)(R₃)(Hphob₂)])linked to the node structure, Z, each via an L₂, and is from zero to 10;L₃ is an independently selected linking group which links Z to cationicgroup —R₄—N—[(R₅)(R₆)(R₇)]; R₄ is an independently selected linear orbranched alkylene (—CH— to —C₆H₁₂—) or monohydroxylalkylene (—CH(OH)— to—C₆(OH)H₁₁(OH)—); R₅, R₆, R₇ are each an independently selected alkyl orgroup containing 1 to 4 carbons (CH₃ to C₄H₉); X₂ is a anioniccounterion or absent; c is the number of (R₄—N—[(R₅)(R₆)(R₇)]) linked tothe node structure, Z, each via an L₃, and is from zero to 10; whereinthe sum of a and b is from 1 to 10 inclusive; the sum of b and c is from1 to 10 inclusive; and the sum of a, b, and c is from 1 to 10 inclusive;provided that: if a+b+c+d is less than or equal to 5, then a+b+c/a+b+c+dis greater than 0.33, or if a+b+c+d is greater than 5, thena+b+c/a+b+c+d is from 0.04 to 0.9.
 2. The compound of claim 1 whereinb=1, the sum of a and b is from 1 to 2, and the sum of b and c is from 1to
 2. 3. The compound of claim 1 selected from the group consisting ofN-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium chloride decaglycerylether; N-(2-hydroxypropyl)-N,N-dimethylcocoalkyl-1-ammonium chloridedecaglyceryl ether; andN-(2-hydroxypropyl)-N,N-dimethylcocoalkyl-2-ammonium chloridedecaglyceryl ether.
 4. The compound of claim 1 selected from the groupconsisting of (N-(2-hydroxypropyl)-N,N-dimethylcocoalkyl-1-ammonium)decaglyceryl monooleate ether;(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium) decaglycerylmonolauryl ether; (N-(2-hydroxypropyl)-N,N-dimethylcocoalkyl-1-ammonium)decaglyceryl monolaurate ether;(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium) decaglycerylmonolaurate ether; and(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium) decaglycerylmonooleate ether.
 5. The compound of claim 1 selected from the groupconsisting of (N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium)(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium) octaglycerylether, and (N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium)(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-2-ammonium) decaglycerylether.
 6. The compound of claim 1 selected from the group consisting of(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium)(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium) decaglycerylmonooleate ether; and(N-(2-hydroxypropyl)-N,N-dimethyllauryl-1-ammonium)(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-2-ammonium) decaglycerylmonooleate ether.
 7. The compound of claim 1 selected from the groupconsisting of (N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium)decaglyceryl monooleate ether;(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-1-ammonium) decaglycerylmonolaurate ether;(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-3-ammonium) decaglycerylmonolaurate ether; and(N-(2-hydroxypropyl)-N,N,N-trimethylpropan-2-ammonium) decaglycerylmonolaurate ether.
 8. A personal care composition comprising: a solvent,a compound of claim 1, and at least one material selected from the groupconsisting of surfactants, chelating agents, emollients, humectants,conditioners, preservatives, opacifiers, fragrances, and combinations oftwo or more thereof.
 9. The composition of claim 8 wherein saidcomposition is substantially free of ethoxylated materials.
 10. A methodof moisturizing or conditioning the skin or hair comprising applying tohair or skin a composition of claim 8.